The stability of water-in-oil emulsions formed during oil slicks or petroleum production operations is ensured by natural surfactant molecules (principally asphaltenes) that are present in the crude oil. These persistent emulsions may be broken by adding a suitable demulsifier at the proper concentration to attain a so-called optimum formulation at which the stability of the emulsion is minimum. In this report, the concentration of asphaltenes is varied by diluting the crude oil with a solvent such as cyclohexane, toluene, or mixtures of them. The experimental evidence shows that there exists some critical asphaltene concentration at which the interfacial zone seems to be saturated. Beyond this threshold, which is typically around 1000 ppm of asphaltenes, the demulsifier concentration necessary to attain the emulsionʼs quickest breaking is constant. Below it, e.g. when the crude is highly diluted with a solvent, the optimum demulsifier concentration is found to be proportional to the asphaltene concentration. The map of emulsion stability versus asphaltene and demulsifier concentrations exhibits a typical pattern for different demulsifiers and diluents, which contributes to improving the interpretation of the demulsifying action.

Seven asphaltene samples and six octylated asphaltene (OA) derivatives were analyzed using laser desorption ionization−time-of-flight (LDI−TOF) mass spectrometry (abbreviated as MS) and vapor pressure osmometry (VPO) techniques. Molecular weight distributions (MWDs) that were determined using MS spanned, for all asphaltenes samples and their octylated counterparts, a similar range, from ∼100 Da to ∼10 000 Da. For asphaltenes, the number-average molecular weight (M n ) and weight-average molecular weight (M w ) afforded values in the 1900 ± 200 and 3200 ± 400 intervals, respectively. Consistently heavier values were observed for the OA derivatives (M n ≈ 2300 ± 200 and M w ≈ 3600 ± 200). To select the adequate laser power for these measurements, experiments at different laser powers were performed, to increase volatility and reduce fragmentation to a minimum. Several other experiments were performed to validate these results. First, good agreement between the measured and calculated M n values was observed for OA materials (calculated from asphaltene M n and n, the number of octyl groups introduced, as determined from elemental analysis); second, M n values, as measured by VPO and MS, were determined to be equal, within an average standard deviation of ±27.0%. These results and calculations strongly suggest that the MWD, the molecular weight range, and the molecular weight averages determined using the present MS technique are reasonable estimates of the molecular weight properties of asphaltenes and not the result of artifacts such as fragmentation, polymerization, incomplete volatilization, etc., which may be occurring during the MS experiment.

Surfactant molecules are tested as water-in-crude emulsion breakers to attain the quickest separation rate in the so-called “proportional regime”. A concept of demulsifier performance is proposed on the basis of the required demulsifier concentration to offset the effect of a given amount of asphaltenes. The experimental evidence allows one to rank the tested products and relate their performance to their hydrophilicity and molecular weight. Some evidence indicates that the presence of acids in the crude makes it easier to break emulsions and suggests that so-called “extended surfactants” can significantly shorten the demulsifying process.

Hydrophilic surfactant molecules with the proper formulation are able to break W/O emulsions stabilized by asphaltenes and other lipophilic amphiphiles as found in the effluent of petroleum wells. The demulsifier performance is here tested according to two critera. The first one, as in previous research, is the minimum dose of demulsifier used to attain the minimum stability at the so-called optimum formulation in a simplified bottle test. The second criterion is the value of this minimum stability at optimum formulation that has a direct relation with the separation time. Our findings show that in a family of ethoxylated surfactants, the best demulsifier is a hydrophilic one, though not too much. When the demulsifier is a mixture of two surfactants, it usually exhibits an intermediate behavior between the components. However, the mixture sometimes appears to be better than any of the components alone with some synergistic effect that improves the performance.

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Resins are reported to be able to contribute to both the stabilization and destabilization of asphaltenes. Resin adsorption isotherms were carried out on different substrates such as silica particles or asphaltenes and silica-asphaltene fraction A 2 complexes extracted from different Venezuelan crude oils, which either show evidence of precipitation problems (Furrial) or do not (Hamaca and Guafita). Experimental evidence indicates that resins from Furrial crude oil display a much higher tendency to adsorb on the different substrates than resins from the two other crude oils, even on silica particles with the same surface area for all of the resins, thus indicating a higher self-interaction. This self-interaction of resin molecules is shown to be the key factor in determining whether these molecules do or do not stabilize asphaltene colloidal particles against aggregation. The experimental results are interpreted according to a simple repulsion/adhesion alternative model.

Asphaltene adsorption from a toluene solution on a glass surface was studied as a function of concentration, at ambient temperature and atmospheric pressure. The thickness of the asphaltene film measured by ellipsometry was found to be in the 20−298 nm range. The film thickness was found to increase by 38−70 nm after 24 h. Solutions containing asphaltene mixtures from different crude oils result in significant variations in film thickness when compared with single asphaltene cases. For CN-Ceuta and DM153-Ceuta mixtures, a diminution was observed, whereas an increase was found with the DM153-Furrial mixture. Finally, the results attained with asphaltenes in which low molecular weight compounds have been removed suggest a film swelling effect due to the alkyl-type resins which are found to modify the colloidal properties of the aggregated asphaltenes in agreement with the literature.

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