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.
Wang, D. (University of North Dakota) | Dawson, M. (Statoil Gulf Services LLC) | Butler, R. (University of North Dakota) | Li, H. (Statoil Gulf Services LLC) | Zhang, J. (University of North Dakota) | Olatunji, K. (University of North Dakota)
With the recent dramatic drop in oil price, production from ultra-tight resources, like the Bakken formation, may drop substantially. Since expenditures for drilling, completion, and fracking have already been made, existing wells will continue to flow, but oil rates will decline—rapidly in many cases. In a low oil-price environment, what can be done to sustain oil production from these tight formations?
We are testing a surfactant imbibition process to recovery oil from shales. We measured surfactant imbibition rates and oil recovery values in laboratory cores from the Bakken shale. After optimizing surfactant formulations at reservoir conditions, we observed oil recovery values up to 10–20% OOIP incremental over brine imbibition. However, whether or not surfactant imbibition will be a viable recovery process depends on achieving sufficiently high oil production rates in a field setting—which requires that we identify conditions that will maximize imbibition rate, as well as total oil recovery. In this paper, we describe laboratory evaluations of oil recovery using different core plugs. These recovery studies involved
(1) surfactant formulation optimization on concentration, salinity and pH, (2) characterization of phase behavior, (3) spontaneous imbibition, and (4) forced imbibition (flooding) with gravity drainage assistance.
In preserved cores, we observed: (1) Formulations using 0.1% surfactant concentration at 4% TDS salinity showed favorable oil recoveries (up to 40% OOIP). (2) Generally, surfactant formulations at optimal concentration and salinity were stable at high temperature (115°C). (3) Injectivity/permeability enhancements up to 75 percent occurred after acidification using acetic acid or HCl. (4) Wettability alteration is the dominant mechanism for surfactant imbibition. Of course, actions that increase fracture width will aid gravity drainage and oil recovery. This information is being used to design and implement a field application of the surfactant imbibition process in an ultra-tight resource.
Imqam, Abdulmhsin (Missouri University of Science and Technology) | Wang, Ze (Missouri University of Science and Technology) | Bai, Baojun (Missouri University of Science and Technology) | Delshad, Mojdeh (The University of Texas at Austin)
Preformed particle gels (PPG) have been successfully applied as a plugging agent to solve the conformance problem in fractured reservoirs. They are injected to plug fractures and then divert displacing fluid into poorly swept zones and areas. However, PPG propagation and plugging mechanisms through open fractures have not been studied thoroughly. This paper investigated the influence of some factors (particle size, brine concentration, heterogeneity, injection flow rate, and brine salinity) on gel injectivity and plugging performance for water flow through opening fractures. Five-foot tubes were used to mimic opening fractures. Three models were designed to gain understanding on how fracture geometry and PPG properties affect gel injection and plugging efficiency, including (1) single fracture with uniform fracture width, (2) single fracture with different widths, and (3) two parallel fractures with different width ratios between each other. Results from single uniform fracture experiments showed that PPG injection pressure was more sensitive to gel strength than gel particle size. When large PPG size and high gel strength were used, high injection pressure and large injection pore volume were required for PPG and brine to reach fracture outlets. Results from single heterogeneous fracture model experiments showed PPG injection pressure increased as the fracture heterogeneity in sections increased. Particle gel accumulated at the choke point within each fracture and caused injection pressure to increase accordingly. Furthermore, results showed that having a lower salinity within a fracture, which was less than the brine salinity that was used to prepare PPG, would improve the PPG plugging efficiency for water flow. Parallel fracture models results showed that when weak PPG was used, a large volume of PPG flowed into a large fracture width and a small portion of the gel particle volume flowed into small fracture width. However, with increased gel strength and fracture width ratio, PPG only flowed through larger fracture widths. This paper demonstrates important impact elements of gel propagation and water flow for different opening fracture situations.
Alexis, Dennis (Chevron Energy Technology Company) | Varadarajan, Dwarakanath (Chevron Energy Technology Company) | Kim, Do Hoon (Chevron Energy Technology Company) | Winslow, Greg (Chevron Energy Technology Company) | Malik, Taimur (Chevron Energy Technology Company)
Performance of current synthetic EOR polymers is primarily constrained by salinity, temperature and shear which restrict their application to low to moderate salinity, low to moderate temperature and relatively high permeability reservoirs. The primary goal of the current work is to qualify recently developed associative polymers (AP) for EOR applications as well as to study their behavior in porous media. We also compare their performance with conventional non-associative polymers. In this work, we present the evaluation of several associative polymers. Two broad types of associative polymers were tested, one with a partially hydrolyzed poly acrylamide (HPAM) backbone and the other with a sulfonated HPAM backbone. The concentrations of the tested polymer vary between 75 ppm and 1000 ppm. We demonstrate the applicability of these innovative AP's through the carefully controlled lab experiments: (1) Corefloods in sandpacks to compare the sweep behaviors with conventional HPAM's. (2) Single phase flooding experiments are carried out in consolidated outcrop rocks to identify optimal polymer concentrations to achieve the desired in-situ resistance. (3) One dimensional displacement experiments with 8 cP and 90 cP oil are carried out in both unconsolidated and consolidated rocks at different temperatures to validate improved oil recovery. Results generally indicate that associative polymers require lower polymer concentration to generate high resistance factors in porous media and have stable long term injectivity behavior in high permeability rocks (>1D). Associative polymers with HPAM backbone have better filterability and injectivity in comparison to those with HPAM sulfonated backbone in low permeability(<300mD) rocks. Improved oil recovery in high permeability rocks compare well with conventional HPAM and sulfonated HPAM polymers. Based on the laboratory results, we are able to establish the selection baseline for associative polymers in different permeability rocks, salinities and temperatures. Such information can be used to select and screen the appropriate associative polymers, resulting in extending their applicability envelope in EOR.
During an Alkaline-Surfactant-Polymer (
In this study, steady-state (
For brine/oil systems some dependence of apparent viscosity on rock permeability was observed; for systems with surfactants no such trend was noticable. The addition of surfactants substantially reduced the apparent viscosities; the viscosity reducing impact of surfactants could be balanced by the addition of polymer. Fractional flow analysis showed that the addition of surfactants reduces the impact of capillary forces resulting in straightened relative permeability curves and higher aqueous phase relative permeability end points.
It is anticipated that this study leads to a fast and fit for purpose characterization method of
Chen, Zhao (New Mexico Inst-Mining & Tech) | Du, Cheng (New Mexico Inst-Mining & Tech) | Kurnia, Ivan (New Mexico Inst-Mining & Tech) | Lou, Junjie (New Mexico Inst-Mining & Tech) | Zhang, Guoyin (New Mexico Petroleum Recovery Research Center) | Yu, Jianjia (New Mexico Petroleum Recovery Research Center) | Lee, Robert L. (New Mexico Petroleum Recovery Research Center)
Hydrodynamic retention is one of the contributors to polymer loss in porous media. In this study, effects of flow rate, polymer molecular weight, and core permeability on hydrodynamic retention were investigated. To quantify hydrodynamic retention, injection of two identical polymer banks at different rates separated by 100 pore volumes of brine flushing was performed. Three HPAM polymers with molecular weights of 6–8 million, 12 million, and 20 million Daltons were tested in a 135 mD sandstone core and xanthan polymer with molecular weight of 2–2.5 million Daltons was tested in an 87 mD sandstone core. The retention of 6–8 million Daltons HPAM in a 1,650 mD sandstone core was also measured. Polymer retention in a fresh core was first measured at low injection rate of 3.11 ft/day. Then, 100 PV of 2% NaCl brine was injected to displace all the mobile polymer molecules in the core till pressure drop across the core became stable. Hydrodynamic retention at elevated flow rates was determined after the completion of retention at lower rates and comparisons with the initial polymer retention were made.
Retention of 96.1 µg/g in the 135 mD core was detected for the 6–8 million HPAM at a flow rate of 3.11 ft/day. Increase of flow rate from 3.11 ft/day to 6.22 ft/day and 12.4 ft/day resulted in incremental retention of 2.27 µg/g and 5.38 µg/g, respectively. The injection of a higher molecular weight polymer at the same rate was performed after retention was satisfied with a lower molecular weight polymer. It was found the degree of hydrodynamic retention was greater when higher molecular weight polymers were injected. When core permeability was changed from 135 mD to 1,650 mD, both the initial and hydrodynamic retention were dramatically decreased. The initial retention of xanthan was 66.7 µg/g in an 87 mD sandstone core, which was smaller compared to the retention of HPAM in the similar core. However, hydrodynamic retention measurements of xanthan gives 3.26 µg/g and 6.38 µg/g increments with the increase of flow rate from 3.11 ft/day to 6.22 ft/day and 12.4 ft/day, which suggested that the retention of xanthan is slightly more sensitive to the change of injection rate than HPAM. This study also implied that measurement of residual resistance factor after polymer injection should be completed after sufficient brine flushing (around 100 PV), otherwise, an overestimated residual resistance factor might be provided.
Polymer flooding is a proven technology to improve sweep efficiency, while being one of the most economical enhanced oil recovery (EOR) processes. Partially hydrolyzed polyacrylamide (HPAM) has been widely used for polymer flooding. As the HPAM usage for EOR increases, the challenge of produced water management is also raised because residual HPAM in produced water could increase total chemical oxygen demand and unwanted viscosity in discharging or re-injecting the water. As the environmental standards and regulations get more stringent, it is difficult for the conventional methods to meet the requirement for discharging. Use of magnetic nanoparticles (MNPs) to remove contaminants from produced water is a promising way to treat produced water in an environmentally green way with minimal use of chemicals. The main attraction for MNPs is their quick response to move in a desired direction with application of external magnetic field. Another attraction of MNPs is versatile and efficient surface modification through suitable polymer coating, depending on the characteristics of target contaminants. In this study, we investigate the feasibility of polymer removal using surface-modified MNPs and regeneration of spent MNPs for multiple re-use.
The electrostatic attraction between negatively charged HPAM polymer and positively charged MNPs controls the attachment of MNPs to HPAM molecular chain; and the subsequent aggregation of the now neutralized MNP-attached HPAM plays a critical role for accelerated and efficient magnetic separation.
Griffith, Nicholas (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Ahmad, Yusra (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Daigle, Hugh (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Huh, Chun (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin)
Interest in silica nanoparticle-stabilized emulsions, especially those employing low-cost natural gas liquids (NGLs), has increased due to recent developments suggesting their use leads to improved conformance control and increased sweep efficiencies. When compared to conventional emulsion- stabilizing materials such as surfactants, nanoparticles are an inexpensive and robust alternative, offering stability over a wider range of temperature and salinity, while reducing environmental impact.
Oil-in-water emulsions with an aqueous nanoparticle phase and either a pentane or butane oil phase at a 1:1 volume ratio were generated at varying salinities for the observations of several emulsion characteristics. The effects of salinity on the stability of silica nanoparticle dispersions and NGL emulsions were observed. Increasing the salinity of the aqueous nanoparticle phase resulted in an increase in effective nanoparticle size due to increased nanoparticle aggregation. Rheology tests and estimates of emulsion droplet sizes were performed. Shear-thinning behavior was observed for all emulsions. Furthermore, overall emulsion viscosity increased with salinity. Nanoparticle-stabilized liquid butane-in-water emulsions were also generated with varying brine concentrations; however, no rheology or droplet size measurements were made due to the volatility of these emulsions.
Residual oil recovery coreflood experiments were conducted (using Boise Sandstone cores) with nanoparticle-stabilized pentane-in-water emulsions as injectant and light mineral oil as residual oil. A recovery of up to 82% residual oil was observed for these experiments. By continuously measuring the pressure drop across the core, a possible mechanism for enhanced oil recovery is proposed. Pentane emulsion coreflood tests indicated that at a slower injection rate, residual oil recovery increases. This contrasts viscous emulsion corefloods (mineral oil or Texaco white oil as the emulsion oil phase), where increasing the injection rate increases the residual oil recovery.
Wettability of the rock is an important parameter in determining oil recovery. It determines the fluid behavior and the fluid distribution in the reservoir. Aging of the rock changes the wettability of the rock and can affect the residual oil saturation. This paper investigates the effect of aging on the oil recovery during the Water-Alternating-CO2 injection (WACO2) process using 20 in. outcrop Grey Berea sandstone cores under immiscible conditions.
In the present work, two coreflood experiments were performed. Both cores were aged for a period of 30 days at 149°F. This study is a continued research and compares the performance of WACO2 injection in aged cores to previously published work with unaged cores. All experiments were done at 500 psi and in the secondary recovery mode. The wettability of the Rock- Brine-CO2-Oil system for aged cores was determined by contact angle measurements using formation brine (174,156 ppm), seawater brine (54,680 ppm) and low-salinity brine (5,000 ppm NaCl). The interfacial tension (IFT) of the Brine-Oil-N2 and Brine-Oil-CO2 system was also measured using the axisymmetric drop shape analysis (ADSA) method. Computerized tomography (CT) scans were obtained for each core in its various states: dry state, 100% water-saturated state, oil saturated state with irreducible water saturation, and residual oil-saturated state. The CT scans were used to determine the porosity profile of the cores.
The contact angle measurements of the Rock - Brine - CO2 - Oil system indicated an increase in contact angles after the aging of the cores. Low-salinity brine showed the most water-wet state (55°) and seawater brine showed the most oil-wet state (96°) of the rock. This may be because of the increased concentration of divalent ions on the surface of the rock during seawater brine injection. Ion binding is the dominant mechanism in the oil-wet nature of the rock. The previously published work stated that the coreflood experiments of the unaged cores resulted in an oil recovery of 61.7 and 64.6% OOIP during low-salinity water-alternating-CO2 and seawater-alternating-CO2 injection, respectively. In aged cores, the oil recovery increased to 97.7 and 76.1% OOIP during the low-salinity water-alternating-CO2 and seawater-alternating-CO2 injection, respectively. The improved oil recovery was attributed to the wettability alteration when the rock was aged.
The interfacial tension measurements of brine/oil/nitrogen and brine/oil/CO2 systems showed that the salinity of the brine had an effect on the IFT. Low-salinity brine (5,000 ppm) yielded the highest IFT values and seawater brine produced the least. Monovalent ions had a weak effect on the interfacial activity between the oil and the brine. When multivalent ions were present, the IFT values were influenced by the salting effect of the brines. During the IFT measurements of brine/oil/CO2 system, the IFT values showed an increasing trend as a function of time and then stabilized. The increase in IFT was because of the initial mass transfer between the CO2, brine, and oil phases.
Water-based polymers are often used to improve oil recovery by increasing displacement sweep efficiency. However, recent laboratory and field work has suggested these polymers, which are often viscoelastic, may also reduce residual oil saturation. The objective of this work is to investigate the effect of viscoelastic polymers on residual oil saturation in Bentheimer sandstones and identify conditions and mechanisms for the improved recovery. Bentheimer sandstones were saturated with a heavy oil (120cp) and then waterflooded to residual oil saturation using brine followed by an inelastic Newtonian fluid (diluted glycerin). These floods were followed by injection of a viscoelastic polymer, hydrolyzed polyacrylamide (HPAM).
Significant reduction in residual oil was observed for all core floods performed at constant pressure drop when the polymer had significant elasticity (determined by the dimensionless Deborah number,