We present a model explaining the mechanism of water-in-oil (W/O) emulsion stabilization in petroleum systems. According to the model, W/O petroleum emulsions are stabilized by at least two types of chemicals: one is a small subfraction of asphaltenes, and the other is a low-molecularweight, surfactant-like material. Their competition for the oil/water interface is based on adsorption kinetics, rather than on differences in adsorption energies. The asphaltenic material adsorbs slowly and irreversibly and forms rigid skins. Surfactant-like species adsorb fast, reaching equilibrium. Both are effective emulsifiers; however, emulsion breaking requires different strategies, depending on the stabilizer.
The need for alkaline conditions in oil sands processing is, in part, to produce natural surfactants from bitumen. Previous studies have shown that the produced surfactants are primarily carboxylic salts of naphthenic acids with the possibility of sulfonic salts as well. The role of these natural surfactants, particularly those in the naphthenate class, is to provide a physicochemical basis for several subprocesses in bitumen extraction. In this study, it was found that the content of indigenous naphthenic acids in bitumen can destabilize, to some extent, the water-in-oil emulsion by lowering the interfacial tension, reducing the rigidity and promoting the coalescence of water droplets.
A major operational issue in the crude oil industry is the formation of intermediate rag layers, (primarily water-in-oil emulsions) in oil−water separation processes that limit the amount and quality of recoverable oil. In this study, the formation of rag layers is evaluated as a function of solvent−bitumen−water ratios, solvent aromaticity, and temperature, with various imaging techniques. Using these techniques, it is possible to obtain an estimate of the amount of oil, water, and asphalthenes in the rag layer and excess phases. On the basis of these material balances, it was observed that when bitumen is diluted with a more paraffinic (poor) solvent, such as Heptol 80/20 (80% heptane and 20% toluene), the asphaltenes in solution tend to adsorb/segregate at exposed oil−water interfaces, impacting the extent of rag layer formation. Diluting similar systems with a more aromatic solvent (Heptol 50/50) reduces the surface activity of the asphaltenes, and the stability of rag layers, as evidenced by lower asphaltene and oil losses to the rag layer. Furthermore, it was observed that increasing the temperature of the system minimizes rag layer formation and the fraction of oil lost to the rag layer. The better separation at high temperature could be explained by the lower viscosity of the oil, which results in improved oil drainage from the rag layer.
Role of bitumen components in stabilization of water-in-diluted oil emulsions was studied using the micropipette technique. Naturally occurring components of bitumen, asphaltenes and maltenes were separated (by precipitating asphaltenes with n-pentane) to investigate their influence on the properties of water drop surfaces in Heptol (a mixture of heptane and toluene at a 4:1 volume ratio). The Heptol-water interfacial tension decreased with increasing adsorption of surface active components from both asphaltenes and maltenes. Rigidity of emulsified water droplet surfaces was observed in the presence of asphaltenes dissolved in Heptol. The observed surface crumpling is attributed to the irreversible adsorption of asphaltenes on the emulsified water droplet in Heptol. Further, the results of droplet interaction experiments indicated that the stability of the water-in-diluted oil emulsions was mainly due to the presence of asphaltenes dissolved in Heptol. However, it was observed that the presence of maltenes can also contribute to the emulsion stability even without welldefined skin formation on the emulsified water droplet surfaces.
Canadian oil sands represent a huge oil resource. Stable water-in-oil (W/O) emulsions, which persist in
Athabasca oil sands from surface mining, are problematic, because of clay solids. This article focuses on the
characterization of water-in-diluted-bitumen emulsions by nuclear magnetic resonance (NMR) measurement
and the transient behavior of emulsions undergoing phase separation. An NMR restricted diffusion experiment
(pulsed gradient spin−echo (PGSE)) can be used to measure the emulsion drop-size distribution. Experimental
data from PGSE measurements show that the emulsion drop size does not change much with time, which
suggests that the water-in-diluted-bitumen emulsion is very stable without an added coalescer. The sedimentation
rate of emulsion and water droplet sedimentation velocity can be obtained from NMR one-dimensional (1-D)
T
1 weighted profile measurement. Emulsion flocculation can be deduced by comparing the sedimentation velocity
from experimental data with a modified Stokes' Law prediction. PR5 (a polyoxyethylene (EO)/polyoxypropylene
(PO) alkylphenol formaldehyde resin) is an optimal coalescer at room temperature. For the sample without
fine clay solids, complete separation can be obtained; for the sample with solids, a rag layer that contains
solids and has intermediate density forms between the clean-oil and free-water layers. Once formed, this rag
layer prevents further coalescence and water separation.
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