The presence of principal ions in the water injected is essential for enhanced oil recovery by formation of water-wet state in carbonates. This study reaffirms this and presents an evaluation of the positive influence of both divalent as wells as monovalent ions on wettability alteration mechanisms during low salinity waterflooding using brines of varying ionic composition, referred to as “smart brines”. Zeta potentiometric analysis and reservoir simulation studies were conducted with diluted and smart brines that were prepared by varying the composition of principal ions. Surface charge of oil-saturated whole core samples of rock in the presence of various diluted and smart brines was estimated by zeta potential measurements. A comprehensive analysis of zeta potentiometric and reservoir simulation studies was done to establish and investigate the linkage between the recovery mechanism and the incremental recovery achieved. It is noted that zeta potential increases with the increasing level of dilution and it can be attributed to electric double-layer mechanism. On the contrary, simulation studies implied a different mechanism where an increase in effluent’s pH and Ca2+ mole fraction along with decrease in moles of minerals and saturation index implied rock dissolution was dominant mechanism. Moreover, the effect of mineral dissolution beyond the injection block is highly doubtful. This study demonstrates that an integrated approach from both zeta potentiometric and simulation studies can be used to provide insights into the underlying science of interactions at pore scale during a low salinity waterflood using smart brines. With the aid of an adequately designed upscaling procedure and protocol, the laboratory results can be further used towards developing field-scale models to obtain with realistic recovery factors with optimized brine composition and salinity.

As carbonate reservoirs are mostly oil-wet, the potential for the success of a waterflooding is lower. Therefore, a primary focus during waterflooding such reservoirs is on the ionic composition and salinity of injected brine which are able to impact the alteration of the rock wettability favorably by altering the surface charge towards a higher negative value or close to zero. The objective of this study is to employ zeta potentiometric studies comprising streaming potential and streaming current techniques to quantify the surface interactions and charges between the carbonate rock and fluid type as a function of the variations in its ionic state and rock saturation. Zeta potentiometric studies were conducted on carbonate rock samples to understand the behavior of different aqueous solutions by variation in the brine's salinity and ionic composition and the results were integrated with wettability studies. The concentrations of potential-determining ions (PDIs) such as SO42-, Mg2+ and Ca2+ in the injected brines are deemed responsible for altering the wettability state of the carbonate rocks. Several diluted brines (25%, 10% and 1% diluted seawater) and smart brines have been investigated. Smart brines were prepared by spiking the concentration of major PDIs. All zeta potential measurements were conducted using a specially designed zeta potentiometer sample-holding clamp capable of using the whole core plugs rather than pulverized rock samples. A major advantage of using the whole core sample is that the same core can be used in subsequent coreflooding tests, thus making zeta potentiometric results more relevant and representative for a particular rock-fluid system used in the study. The classical streaming potential and streaming current techniques were used for zeta potential measurement. The Fairbrother-Mastin approach was used where the streaming potential is measured against different pressure differentials. Measurements were also carried out for brines with rock samples of different states: oil-saturated, water-saturated and rock samples cleaned with organic solvents to determine any likely variations in surface charge interactions. The results of our experiments imply that the value of zeta potential either increases or becomes more negative with increasing percentage of dilution (25%, 10%, and 1%). This can be attributed to electrical double-layer expansion which is primarily caused by reduced ionic strength. Furthermore, with measurements done on smart brines, zeta potential value was also found to be increased when different diluted brines are spiked with ionic concentration of PDIs such as sulfate. This could have been caused by surface ion alteration mechanism where PDIs get adsorbed on rock surface causing possible detachment of oil droplets. Both the phenomena are known mechanisms for altering wettability towards more water wetness in carbonate rocks and are discussed in detail.

Characterization of the rock and fluids is an essential step in screening a reservoir for Low-Salinity Water Flooding (LSWF). A detailed characterization of rock and fluid properties using appropriate methods is being presented for LSWF in a low-permeability deep carbonate reservoir together with a critical analysis of findings. The techniques used are assessed against other possible alternative methods, with inferences drawn on advantages and disadvantages of each to better interpret and apply data so gathered. In so doing, discussions on their key features as to how they can be used effectively and efficiently to screen a reservoir for LSWF are also provided. Such integration of results with other available reservoir and production data should result in a comprehensive description of the target reservoir, and it will help interpret the mechanisms and process dynamics more reliably during a low-salinity waterflood. This integration should allow us not only to gain confidence on the experimental studies but could also help optimize the key parameters responsible for formulating a more robust, reliable and representative regime for tests relevant to the LSWF prior to its eventual implementation in the field. To authors’ knowledge, such integration of experimental studies has not yet been reported in the literature, particularly for the tight carbonate reservoirs with highly paraffinic oil.

The study of zeta potential using electro‐kinetic analyzers that measure streaming potential has limitations of measurements to relatively low ionic strength solutions (<0.1 mol/L) due to the threshold limit of streaming potential signal above a certain limit of ionic strength. The objective of this study is to indirectly estimate the zeta potential for higher salinity brine using the zeta potential measurements for low salinity brine, develop an understanding of electrostatic shielding as predicted by the electric double layer (EDL) model, and overcome the limitation of the apparatus. Zeta potential become less negative as ionic strength increases, as per the Gouy–Chapman–Stern theory. It explains the suppression of electro‐kinetic phenomena due to the gradual compression of the diffuse layer. Our calculations show that the zeta potential and the Debye length become nearly constant at higher ionic strength. The ability to estimate zeta potential by the Gouy‐Chapman‐Stern theory at increasing ionic strength is limited. This theory predicts that the concentration of counter‐ions in the Stern layer increases with increasing ionic strength of the brine until the surface charge becomes neutralized and the diffuse layer collapses. However, it ignores the spatial extension of ions. It considers them as a point charge and may not accurately predict the zeta potential at higher ionic strength. The extent of diffuse layer compression is thus limited to the size of the hydrated counter‐ion. It is very unlikely that the measured zeta potential will become zero at higher ionic strength of brines and our calculations show the same.

This study focusses on the investigation of wettability alteration behavior during low salinity waterflood (LSWF) process in a tight carbonate reservoir through Zeta potential studies in conjunction with spontaneous imbibition tests and estimation of the contact angle between the wetting fluid and the rock surface. This will help in understanding the role rock-oil-brine interactions play during an LSWF process. The classical streaming potential technique were used to determine Zeta potential. Measurements were carried out with diluted brines using different rock samples of in two states: oil-saturated and brine-saturated. The experimental results imply that the value of zeta potential becomes more negative with increasing percentage of dilution (25%, 10%, and 1%). This is attributed to electrical double-layer expansion which is caused, primarily, by the reduced ionic strength. We concluded that rock saturated with oil may give an insight on oil rock interactions while the rock saturated with brine may give insight on rock-brine interactions. The dilution of water helps increase the electrostatic repulsive forces between the two interfaces, which in turns, leads to the incremental recovery during LSWF process. This observation was also confirmed by coreflooding and wettability experiments through spontaneous imbibition tests and contact angle measurements conducted using the same oil-brine-rock systems. This is an investigative study of oil-brine-rock interaction behavior during a LSWF process that is difficult to accomplish through and during a conventional coreflooding displacement test. In addition, this study also couples the relationship between the wettability alteration and oil-brine-rock interactions during an LSWF process.