Effect of different polar organic compounds on wettability of calcite surfaces

The average oil recovery by conventional water flooding from oil-wet and naturally fractured carbonate reservoirs is often less than 30%. Removal of adsorbed acidic components and/or asphaltene from the carbonate surface results in wettability alteration towards water-wet which is an effective approach to enhance oil recovery. Long chain fatty acids, long chain naphthenic acids and asphaltene are major components in crude oil which are responsible for wettability alteration in carbonate reservoirs while unsaturated acids have minor effect. In this study, a more accurate quantification of the effects of different types and structures of polar components that contribute to the initial oil-wetting extent of the reservoir rocks were used (aliphatic saturated acids, aliphatic unsaturated acids, naphthenic acids, aromatic acids and asphaltene). Different analytical tools (contact angle, zeta potential, Fourier transform infrared spectroscopy and thermal analysis) were utilized for all acids in order to study surface characteristics. The results indicated that polar organic compounds act in different ways according to their structure and properties. Presence of double bond could make the acid molecule more polar, reactive and less hydrophobic. In addition, it can affect the spatial arrangement of the molecule and hence its orientation on the surface. Presence of benzene ring increases the reactivity and polarity of carboxylic group. Moreover, it enhances hydrophilic properties of the acid due to electrons of π double bonds that can resonate over aromatic carbon atoms. The results revealed that, in the presence of water film, combination of acid dissociation in water, surface activity of acid and water solubility controls the acid adsorption and hence wettability alteration of the surface during aging process. Chemisorption of carboxylic acids/asphaltene changes the wettability of calcite surface. In addition to chemical adsorption, some acids adsorb physically on the surface. Physical adsorption of polar compounds may happen via hydrogen bonding between carboxylic groups and carbonate ions on the surface. Although physical adsorption is reversible and forms weak bonds between adsorbate and adsorbent, it may partially contribute to wettability alteration.