Fatty Acid-Asphaltene Interactions at Oil/Water Interface Xi Wang, Erica Pensini and Zhenghe Xu * Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, T6G 2V4, Canada # Sharath Chandra Mahavadi, Simon Ivar Andersen, and Wael Abdallah , Schlumberger, DBR Technology Center, Edmonton, AB, T6N 1M9, Canada # Schlumberger Dhahran Carbonate Research Center, Dhahran, East Province, 31942, Saudi Arabia Jan M. Buiting, Saudi Aramco, Dhahran, Saudi Arabia (*Corresponding author: [email protected]) Asphaltenes have been shown to stabilize the water-in-oil emulsions by forming a viscoelastic interfacial film via molecular aggregation at the oil/water interfaces. Natural carboxylic acids and their anions present in crude oil are able to compete with asphaltenes to adsorb at the crude oil/water interface, decreasing significantly the crude oilwater interfacial tension. In this study, we designed a group of experiments that systematically probe the molecular interactions of naphthenic acid with asphaltenes at the oil/water interface by determining the Langmuir interfacial isotherms and measuring the crumpling ratio of water droplets in crude oil. Figure 1 shows that stearic acid alone is not able to form rigid films at the toluene/water interface, while asphaltenes form more rigid interfacial films. Upon mixing of asphaltenes with stearic acids, non-ideal (non-additive) behavior of interfacial isotherms was observed. Stearic acid was found to soften the asphaltene films and make the films more expanded and flexible at the interface. The rigidity of the interfacial films was found to be directly proportional to the amount of the stearic acid present in the system. Washing experiments of the top phase with solvent showed that both asphaltenes and stearic acids adsorbed irreversibly at the toluene/water interface. Experiments conducted by diffusion of asphaltenes and stearic acids revealed that the stearic acid is less likely to adsorbed at the interface than asphaltenes. However, the general trend of non-ideal adsorption isotherms is the same as in the case of spreading experiments. Crumpling experiments were conducted for the same systems. The crumpling ratio results in Figure 2 support general conclusions derived from Langmuir interfacial isotherm measurements, showing a decrease in film rigidity with the addition stearic acid. In conclusion, the results from this research provide a more accurate picture on the role of surface active organic acids in stabilizing oil-water petroleum emulsions. Figure 1: Isotherms measured with 12 ml (1 mg/ml) asphaltenes and 48 ml (1 mg/ml) stearic acid at the toluene/water interface, showing the synergy (nonadditive) in increasing interfacial activity and film rigidity. Asphaltene Asphaltene+ Stearic acid Stearic acid Before Crumpling After Crumpling Figure 2: Crumpling of water droplets in toluene, illustrating the decrease in crumpling by stearic acid addition.
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