SmartWater flooding through injection of chemistry optimized waters by tuning individual ions is recently getting more attention in the industry for improved oil recovery in carbonate reservoirs. Most of the research studies described so far in this area have been limited to studying the interactions at rock-fluids interfaces by measuring contact angles, zeta potential, and adhesion forces. The other widely reported interfacial tension data at oil-water interfaces do not consider the formation of interfacial monolayer and the interfacial tension is estimated as an average parameter relying on the properties of two individual bulk phases. As a result, such measurements have serious shortcomings to provide any details on complex microscopic scale interactions occurring directly at the interface between crude oil and water to understand the SmartWater flood recovery mechanism.
In this study, two novel interfacial instruments of interfacial shear rheometer and surface potential sensor were used to study microscopic scale interactions of various individual water ions at both air-water and complex crude oil-water interfaces. The measured interfacial rheology data indicated totally different interfacial behavior at crude oil-water interface when compared to air-water interface due to presence of crude oil functional groups. Viscous dominated response was observed at crude oil-water interface for all brine compositions. These interfaces behaved like a viscous fluid without exhibiting viscoelastic solid like properties. Lower interfacial viscous modulus was observed for certain key ions such as calcium, magnesium, and sodium. The interfacial viscous modulus was found to be substantially much higher for sulfates, besides exhibiting some elasticity. The surface potential was gradually decreased by replacing seawater with calcium only brine. The better surface activity with seawater can be attributed to adsorption of more key water ions at the surface.
The interesting results observed with certain water ions at fluid-fluid interfaces are expected to work in tandem with rock-fluids interactions to impact oil recovery in SmartWater flood. At first, they play a role to control the accessibility of active water ions to approach the rock surface, interact with it and subsequently alter wettability. Next oil droplets adhering to the rock surface will be detached and released due to favorable interactions occurring at rock-fluids interfaces. The interfacial film between oil and water can then quickly be destabilized due to less viscous interfaces observed with certain ions to promote drop-drop coalescence and easy mobilization of released oil droplets. This coalescence process is sequential and it would continue until the formation of small oil bank.
This is the first study that showed added importance of fluid-fluid interactions in SmartWater flood by using direct measurements on individual water ions at crude oil-water interface. In addition, a new oil recovery mechanism was proposed by combining both the interactions occurring at fluid-fluid and rock-fluids interfaces. The new fundamental knowledge gained in this study will provide an important guidance on how to synergize water ion interactions at fluid-fluid interfaces with those at rock-fluids interfaces to optimize oil recovery from SmartWater flood.
Prieto, C. A. (CEPSA Research Center) | Rodriguez, R. (CEPSA Research Center) | Romero, P. (CEPSA Research Center) | Blin, N. (CEPSA Research Center) | Panadero, A. (CEPSA Research Center) | Escudero, M. J. (CEPSA Research Center) | Barrio, I. (CEPSA Research Center) | Alvarez, E. (CEPSA Research Center) | Montes, J. (CEPSA EP) | Angulo, R. | Cubillos, H.
The design of an alkali-surfactant-polymer (ASP) formulation for chemical Enhanced Oil Recovery poses multiple challenges from the experimental point of view. The present research examines the laboratory procedures and experimental results aimed at selecting the most suitable chemicals for an ASP pilot trial at the Caracara Sur field (Los Llanos Basin, Colombia). The key challenge was the limited compatibility of the surfactant and polymer selected under reservoir conditions (temperature and total salinity), leading to phase separation of the ASP solution and losses of the activity of both chemicals. An extension of the experimental program was required to re-design the formulation and mitigate risks of damaging the formation in the following field trials. The formulation comprised an alkyl benzene sulfonate as main ingredient, a hydrolyzed polyacrylamide as viscosifying agent and some weak alkali to reach the optimum salinity of the mixture. A mono-alkyl diphenyl disulfonate ether was added as coupling agent to improve compatibility of the ASP mixture. The performance of the selected ASP formulation was assessed by means of interfacial tension measurements, long-term thermal stability tests and dynamic core-flooding tests. The formulation provided ultra-low interfacial tension (< 10-2 mN/m) and viscosity enough to assure an appropriate mobility control. Hence, the formulation was considered to be suitable for further testing in the field pilot.
Scaling up from lab to pilot is one of the challenges to meet in any ASP project to accomplish the requirements at full implementation. Tailored EOR surfactants developed and manufactured in the laboratory, to achieve the lowest interfacial tension (IFT) between oil and water at the reservoir conditions, have to be viable and robust in the manufacture, capable in performance and compatible in the formulation, not only at laboratory scale, but also at industrial scale.
It is described in this poster the route map in the development and manufacture of alkyl aryl sulfonates surfactants for the Cepsa ASP pilot project in the Caracara Sur field, Los Llanos basin (Colombia) from a continuous feed-back of the laboratory tests. The surfactant employed for the project was selected from other surfactants from several suppliers and dyalkylbenzene sodium sulfonate was the one achieving the lowest interfacial tension for Caracara field conditions. The dyalkylbenzene sodium sulfonate was accompanied by a co-surfactant improving the solubility and performance properties.
Pilot ASP injection started in May 2015 and some conclusions were obtained during the production of the surfactants in several manufacture batches: Composition, molecular weight even isomerism of alkylbenzenes may impact strongly on the interfacial activity of alkyl aryl sulfonates surfactants. Sulfonation and neutralization of alkylbenzenes are critical processes to comply the requirements of alkyl aryl surfactants for any cEOR project. Finally, the laboratory in the field for quality assurance and quality control (QA/QC) of surfactants is completely necessary. Periodical sampling and on-site analyses are scheduled but also samples delivery to research center for more sophisticated analyses. These data are essential for the final performance evaluation and the project success.
Composition, molecular weight even isomerism of alkylbenzenes may impact strongly on the interfacial activity of alkyl aryl sulfonates surfactants.
Sulfonation and neutralization of alkylbenzenes are critical processes to comply the requirements of alkyl aryl surfactants for any cEOR project.
Finally, the laboratory in the field for quality assurance and quality control (QA/QC) of surfactants is completely necessary. Periodical sampling and on-site analyses are scheduled but also samples delivery to research center for more sophisticated analyses. These data are essential for the final performance evaluation and the project success.
Recovery from oil reservoirs could be improved by lowering the injection water salinity or by modifying the water injection chemistry. This has been proposed as a way to increase rock water-wetness. However, we have observed that the presence of sulfate anions in the aqueous phase can change the crude oil-water interfacial rheology drastically, and as a result, the oil recovery factor could be increased solely by alteration of fluid-fluid interactions. The purpose of this research is to show the effect of sulfate anion concentration in seawater injection on oil production through coreflooding results at low temperature.
Interfacial rheological experiments were run with several crude oils and modified seawater to see the effect of different ions on visco-elasticity of the crude oil-brine interface using an AR-G2 rheometer with a dual-wall ring fixture. Based on previous experimental results, carefully selected coreflooding experiments were run to evaluate differential pressure and oil recovery for each selected brine. Coreflooding experiments used Indiana Limestone at 25°C without aging to minimize changes in rock wettability.
The interfacial rheological results show that the visco-elasticity of the crude oil-brine interface is higher for a low-salinity brine compared to a higher-salinity one when individual salts are used, e.g. NaCl or Na2SO4. The difference is more pronounced if ultralow salinities are compared. For the cases with salinity values similar to that of seawater, the effect of sulfate concentration in water on interfacial visco-elasticity is more noticeable. Coreflooding results show that brines with a higher visco-elasticity, corresponding to a higher sulfate concentration in the water injected, yield higher oil recovery factor that those with lower visco-elasticity, including the experiments with salinity lower than 50% of that of seawater. Brine-rock reactions were geochemically simulated to prevent injection conditions that could cause formation damage. Additionally, pH, electrical conductivity and total dissolved solid (TDS) were analyzed in the effluents. Results show that for the model rock used, brine composition does not change significantly from contact with rock surfaces. Since wettability alteration was minimized by use of low-temperature and short ageing time, recovery correlates better with changes in interfacial rheology. For results showing an apparent lack of correspondence with the interfacial rheological response, arguments based on ganglia dynamics might shed light on the observed recovery outcome.
Our findings reveal that the injection of water with sulfate can modify the fluid-fluid interactions and consequently the final oil recovery, so in some cases, low-salinity brine injection is not necessarily conducive to an increment in oil production. Findings also indicate that more characterization of the brine-crude oil interface should be carefully conducted as part of the screening of adjusted brine chemistry waterflooding.