This contribution focuses on surface complexes in the calcite-brine-surfactant system. This is relevant for the recovery of oil when using a new hybrid enhanced oil recovery (EOR) method, which combines smart-water (i.e., ionically modified brine) and foam-flooding (SWAF) of light oil with dissolved carbon dioxide (CO₂) at high pressure in carbonate (i.e., calcite) reservoirs. Using this new hybrid EOR-method (i.e., the SWAF-process) is not only economically attractive (i.e., it reduces opex costs) but also enhances the effectiveness of the production process, and thus reduces the environmental impact. Ionically modified brine (i.e., low-salinity) has a dual improvement effect. It not only leads to more stable foam lamellae, but also helps to change the carbonate rock wettability, leading for some conditions to more favorable relative permeability behavior. The mechanism for the modified permeability behavior in the presence of ionically modified brine is only partly understood. Therefore, we study this process initially in a zero dimensional (thermodynamics) setting, which can be used for the one dimensional (1D) displacement process with an oleic phase that contains carbon dioxide (CO₂) and an aqueous phase that contains both carbon dioxide (CO₂) and all the ionic substances. Using DLVO theory and surface complexation modeling to better understand the mechanism(s) of ionically modified brine as wettability modifier and foam stabilizer. We perform simulations using both (NaCl) and (MgCl₂) to show the effect of a divalent ion at the high-salinity (8500 mmol/kg-w) and low-salinity (0.4 mmol/kg-w) for both ambient-conditions at (25°C) and at the reservoir-conditions (80°C). We confine our analysis to a description that uses the Dzombak-Morel model of surface complexes, which is based on the Debye-Hückel theory (i.e., valid up to ionic strength of 0.3 (mol/kilogram of water)). We also investigate the effect of carbon dioxide (CO₂) on the stability of low-salinity foam-laminae. We model the foam-laminae, which contain as surface complex a (cationic) surfactant in an aqueous phase. We use the PHREEQC-software to calculate the surface charge and the surface potential. The presence of a carbon dioxide (CO₂) phase leads to dissolution of four valent C(IV) compounds in the aqueous film. PHREEQC also calculates the equilibrium concentrations and surface potential and allows the study of the effect of salinity and the carbon dioxide (CO₂) gas pressure. For the soap-film (foam-film) in a carbon dioxide (CO₂) atmosphere we do use Pitzer activity coefficients (i.e., valid up to 6 (mol/kilogram of water)). As our aim is to show the methodology and the versatility of this approach, we leave more realistic choices of these parameters for future work.sFor the conditions considered we can qualitatively state that, in the presence of (NaCl i.e., at pH > 10) and (MgCl₂ i.e., pH > 10.3), the low-salinity case shows a more stable water-film behavior at (25°C) and at (80°C) than the high-salinity case for both (25°C) and (80°C). Moreover, high carbon dioxide (CO₂) pressures have a destabilizing effect on the film, as they reduce the surface potential. A reduced surface potential leads to a decreasing electrostatic double layer repulsion and thus destabilizes the foam-film, whereas low-salinity leads to less screening of the surface potential and thus improves the stability of the foam-film. The low-salinity flow is characterized by a high residual oil saturation and low end-point permeability for the two phase oil-water flow. This leads to a more favorable mobility ratio and thus a more favorable displacement process. For the calcite surface an enhanced stability helps to stabilize the water film on the calcite surface if the oil-water surface charge has the same sign as the surface charge on the calcite surface. Our calculations show the pH range where the sign of these charges is the same or opposite at low-salinity and high-salinity conditions. Admittedly these calculations only show trends, but can be used to delineate optimal conditions for the application of “Smart Water Assisted Foam (SWAF) Flooding”. It is expected that the SWAF-process under the optimum conditions will make the proposed new hybrid Enhanced Oil Recovery (EOR) process environmentally and economically attractive. ... Read more

This paper deals with on line viscosity measurements using integrated circuit technology, and is building on a previous paper on the use radio frequency identifier (RFID) technology for determining dielectric coefficients. It is asserted that the progress in RFID technology and integrated circuits, in particular in micro–electro–mechanical system (MEMS) makes it possible to combine them to perform physico-chemical property measurements using devices on centimeter scale. It can even be expected that these devices can be made increasingly smaller. An important property of interest is the viscosity, in this specific case, for the use of Arabic gum in enhanced oil recovery. Arabic gum, is an environmentally acceptable natural product. Natural-polymer solutions 1000 [ppm] are more viscous and therefore more efficient oil displacement agents. They require less invested exergy than non-viscosified water to recover oil. However, polymers, in particular environmentally acceptable natural-polymers (e.g., Guar–Arabic gum) available in large quantities in India and Sudan, are susceptible to microbial degradation. It is therefore important to monitor its quality at the injection and production side for real-time quality control. Natural-polymers based on plant products are promising EOR agents. They may have a lower environmental footprint because of the biodegradability. To provide a proof of concept, we use a state of the art acoustic wave sensor (AWS), which can determine acoustic viscosities. It is asserted that RFID technology can be used to record the acoustic wave signal (SenGenuity vismart acoustic wave Sensor AWS) to determine the viscosity at some distance (meters) away from the measurement device. A calibration with solutions of known viscosity behavior (i.e., Glycerol) can be used to relate the acoustic viscosity to the dynamic viscosity. We can calibrate the acoustic wave sensor using Guar–Arabic gum solutions to measurements with the Anton Paar viscometer (MCR-302). For the glycerol solution we also compare to reported literature data. The Newtonian viscosity measurements of the Paar density meter, and the literature values agree within a few percent. These favorable comparisons, are an important step in developing a methodology that allows cutting edge RFID-IC technology for real-time non-contact monitoring of viscosity degradation. ... Read more

It has been estimated that 17% of the recovered hydrocarbon exergy in oil fields [1]is spent on fluid handling and recovery costs. Therefore, improving the efficiency of oil production can give an some contribution to more efficient energy usage and therefore minimizing to some extent the carbon footprint. By way of example we present in this paper a work-flow, which can serve as a template for computing the fluid handling and recovery costs for natural polymer (Guar-Arabic Gum)flooding. The main contributors to the exergy investment in an Exergy Return on Exergy Investment analysis (ERoEI)are, the fluid circulation costs, the steel costs of the tubing and casing and to some degree the drilling costs. The main contributor to the exergy gain is the exergy of the produced oil. The fluid circulation costs represent the largest exergy investment and usually approximately accounts for 80% of the exergy used for the recovery of oil. For quantifying the circulation costs, the paper uses a 1-D displacement model of polymer flooding of oil to compare the enhanced oil recovery (EOR)history for three scenarios, i.e., (1)water injection, (2)natural-polymer water injection and (3)natural-polymer slug injection. The advantage of a 1-D model is that it allows multiple comparisons of many scenario's avoiding time consuming simulations but this goes at the expense of ignoring 3-D effects. The 1-D model can be extended to a 2-D or 3-D model, which makes it possible to include the improvement of vertical and areal sweep-efficiency. A numerical solution of the EOR model is obtained with COMSOL. We analyze the exergy balance of viscosified water, e.g., with natural-polymer. A comparison as to the displacement efficiency is made between the three scenarios, viz., water, Guar-Arabic gum, and slug injection. The viscosity behavior of Guar-Arabic gum is obtained from laboratory data. It is argued that an ERoEI analysis, which is used on its own or complementary to an economic analysis, can be used to show the advantage of using Guar-Arabic gum slugs with respect to permanent polymer-injection to enhance the oil recovery. Moreover, the analysis shows that at the end of the project, the concept of exergy-zero recovery time or zero-time marks, for each scenario the termination point, i.e., when the circulation exergy costs (exergy investment)become equal to the recovery exergy (exergy return), and thus recovery should be abandoned. For the conditions considered a single polymer injection displacement leads to optimal results. ... Read more