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.
Improved Oil Reocvery (IOR) technologies may offer a new strategy to improve the initial production (IP) and slow the production decline from oil-rich shale formations. Early implementation of chemical IOR technologies largely have been overlooked during strategic planning of unconventional reservoirs. The purpose of this study is to improve understanding of the dynamic processes of oil displacement by surfactants and to investigate mechanism of how surfactants extract oil. A successful conventional surfactant "huff-n-puff' treatment is described with a focus on any relationship between increased oil production and the surfactant soaking period. Surfactant chemistry has been considered as one of a few ultimate IOR solutions. Despite being well proven as effective chemicals to recover oil from convenetional reservoris, surfactants commonly are used in hydraulic fracturing of unconventional reservoris are just to promote flow back of the injected aqueous fluid over a relatively short time frame. In order to better understand the functionality of surfactants for obtaining favorable oil interaction with both the stimulation fluid and rock matrix, a specifically-designed "oil-on-a-plate" (OOAP) setup and procedure is employed to examine the penetration of surfactant into the oil-film that is adhereing to a solid surface. In addition to the well-recognized spontaneous imbibition and surface wettability alternation processes, surfactant also can gradually penetrate and mobilize oil droplets, resulting in improved oil recovert. If properly selected and designed, the surfactant additives in stimulation/fracturing fluids could have multi-functions towards improving both IP and the longer-term oil production. Besides serving as a demulsifier and flowback enhancer to boost IP, the surfactants could continuously lift-up and mobilize adsorbed oil to increase recoverable oil in place.
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.
Post-fracturing production data analysis indicates stimulation of some west Texas wells with surfactant additives did not enhance production as high as expected. Analysis of flowback and produced water for surfactant residues revealed 99% of surfactant was retained inside wells (
Literature precedent exists that polyelectrolyte (PET)-based SAs could significantly reduce surfactant adsorption not only onto a variety of outcrop minerals (Carlpool dolomite, calcite, kaolinite, Berea sandstone, Indiana limestone, etc.) and metal oxide nanoparticles, but also unconventional shale formulations in which surface area can be up to 700 m2/g. In this study, the adsorptions of surfactant and SA to proppants were first examined. Results indicate no adsorption was observed to proppant for both surfactants and PET-based SAs. SAs (0.5 to 1 gal/1,000 gal (gpt)) were then injected with surfactant (1 to 3 gpt) at an appropriate ratio into column-packed shale formulations (primarily composed of calcite, dolomite, quartz, illite, pyrite, and plagioclase feldspar) to investigate its effectiveness in controlling surfactant retention caused by adsorption. Laboratory testing revealed injection of 3 gpt mixture of surfactant and SA has a similar adsorption profile (surface tension as a function of time) as 3 gpt surfactant alone based on the dynamic surface tension measurement. Notably, the addition of SAs resulted in lower surface tension and enhanced hydrocarbon solubility; and thus, an improved oil recovery by surfactant was achieved as evidenced by the oil recovery tests. Additionally, 68% friction reduction of the fracturing fluid with surfactant and SA was sufficient for the field operation compared to the guar-based fluid used in the hydraulic fracturing applications.
As a result of the laboratory findings, field trials were executed on a three well pad in the Permian basin (PB). For the first 30 days oil and gas production appeared to be significantly higher than the average production from offset wells in the same area that were previously fractured with the same surfactant.
A systematic approach to characterize the mixed wet configurations of various reservoir rocks (sandstone and carbonates) by evaluating their surface energy distributions has been presented in this paper. This approach was tested against the macroscopic spatial distribution of oil-wet and water-wet sites and at different temperatures for validation.
The new approach used to characterize the mixed wettability of a reservoir rock pertains to establishing a relation between the volume fraction of the mixed-wet reservoir rocks and surface energy of the mixture. This approach is based on an accurate description of the various physico-chemical interfacial forces present at the reservoir rock surface using Inverse Gas Chromatography (IGC). Mixed-wet configurations of various reservoir rocks are created by combining water-wet and oil-wet samples of the rock in different volume fractions and shaken together to establish uniform distribution. These samples are then subjected to the IGC analysis at different temperatures to deduce their surface energy distribution. The relation developed herein is tested against spatial heterogeneity by combining the oil-wet and water-wet rock samples in a layered fashion to validate the approach. The complete method to deduce the surface energy distribution of a rock surface using IGC has also been explained in detail.
A definite and conclusive relationship between the surface energy and mixed wettability of silica glass beads, calcite, and dolomite samples was established in this study. The mixed-wet configurations of the rock samples ranged from 0% oil-wet (meaning water-wet samples) to 100% oil-wet samples. The findings indicated that the Lifshitz-van der Waals component of the rock mixture did not undergo any change with change in the wetting state of the system under study. However the acid base components showed a marked decrease with increasing oil wetness before plateauing. Temperature was found to have a profound impact on the surface energy of a rock surface. Spatial heterogeneity by way of layered and segregated distribution of oil-wet and water-wet sites did not affect the eventual surface energy distribution thereby validating the new approach.
Kim, Ijung (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Worthen, Andrew J. (McKetta Department of Chemical Engineering, The University of Texas at Austin) | Lotfollahi, Mohammad (Department of Petroleum and Geosystems Engineering, The University of Texas at Austin) | Johnston, Keith P. (McKetta Department of Chemical Engineering, The University of Texas at Austin) | DiCarlo, David A. (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)
The immense nanotechnology advances in other industries provided opportunities to rapidly develop various applications of nanoparticles in the oil and gas industry. In particular, nanoparticle has shown its capability to improve the emulsion stability by generating so-called Pickering emulsion, which is expected to improve EOR processes with better conformance control. Recent studies showed a significant synergy between nanoparticles and very low concentration of surfactant, in generating highly stable emulsions. This study's focus is to exploit the synergy's benefit in employing such emulsions for improved mobility control, especially under high-salinity conditions.
Hydrophilic silica nanoparticles were employed to quantify the synergy of nanoparticle and surfactant in oil-in-brine emulsion formation. The nanoparticle and/or the selected surfactant in aqueous phase and decane were co-injected into a sandpack column to generate oil-in-brine emulsions. Four different surfactants (cationic, nonionic, zwitterionic, and anionic) were examined, and the emulsion stability was analyzed using microscope and rheometer.
Strong and stable emulsions were successfully generated in the combinations of either cationic or nonionic surfactant with nanoparticles, while the nanoparticles and the surfactant by themselves were unable to generate stable emulsions. The synergy was most significant with the cationic surfactant, while the anionic surfactant was least effective, indicating the electrostatic interactions with surfactant and liquid/liquid interface as a decisive factor. With the zwitterionic surfactant, the synergy effect was not as great as the cationic surfactant. The synergy was greater with the nonionic surfactant than the zwitterionic surfactant, implying that the surfactant adsorption at oil-brine interface can be increased by hydrogen bonding between surfactant and nanoparticle when the electrostatic repulsion is no longer effective.
In generating highly stable emulsions for improved control for adverse-mobility waterflooding in harsh-condition reservoirs, we show a procedure to find the optimum choice of surfactant and its concentration to effectively and efficiently generate the nanoparticle-stabilized emulsion exploiting their synergy. The findings in this study propose a way to maximize the beneficial use of nanoparticle-stabilized emulsions for EOR at minimum cost for nanoparticle and surfactant.
Depth to Surface Resistivity (DSR) has been shown to be effective at mapping CO2, water flood, and residual oil aerially and vertically. Provided there is sufficient resistivity contrast between injected and in-situ fluids and subject to the reservoir depth and overburden resistivity, the technique is applicable for monitoring IOR/EOR fields. This information can be used to evaluate cap rock integrity, fluid loss to faults, and migration paths. The following paper presents a study of a CO2 flood followed by water alternating gas (WAG) injection.
Wang, Haitao (Petroleum Exploration & Production Research Institute, Sinopec) | Lun, Zengmin (Petroleum Exploration & Production Research Institute, Sinopec) | Lv, Chengyuan (Petroleum Exploration & Production Research Institute, Sinopec) | Lang, Dongjiang (Petroleum Exploration & Production Research Institute, Sinopec) | Pan, Weiyi (Petroleum Exploration & Production Research Institute, Sinopec) | Luo, Ming (Petroleum Exploration & Production Research Institute, Sinopec) | Wang, Rui (Petroleum Exploration & Production Research Institute, Sinopec) | Chen, Shaohua (Petroleum Exploration & Production Research Institute, Sinopec)
Nuclear magnetic resonance (NMR) was used to investigate the exposure between CO2 and matrix with permeability of 0.218 mD at 40 °C and 12 MPa. Before NMR experiment, the core was saturated with oil. To investigate the effects of exposure time on EOR, the saturated core was exposed to CO2 and T2 test was continuously performed with NMR system until the obtained T2 spectrum was unchanged. After the first exposure, CO2 and matrix reached equilibrium state. The second exposure started when CO2 injection was under a constant pressure of 12 MPa and at a constant rate to keep fresh CO2 in system. The procedure of T2 test was unchanged. The third and fourth exposures were conducted in sequence. The results showed that (1) Oil in all pores can mobilize as exposure time increases. (2) The recovery is 46.6% for oil in pores with the diameter of pore larger than 1 µm, this result is higher than the recovery (12.8%) for oil in pores with the diameter of pore smaller than 1 µm. (3) Recovery can be divided into two stages according to the exposure time: a fast-growing stage and a slow-growing stage. (4) Initially, the oil exists in pores with maximum radius of 21 µm in the originally saturated core. After CO2 injection, oil flows to pores with radius greater than 21 µm, suggesting that oil in tight matrix "diffuses" to the surface of core with exposure between CO2 and matrix. (5) The final recoveries of 1st, 2nd, 3rd, 4th exposure experiments are 23.7%, 7.2%, 2.6% and 1.5%, respectively.
Piñerez T., Iván D. (University of Stavanger) | Austad, Tor (University of Stavanger) | Strand, Skule (University of Stavanger) | Puntervold, Tina (University of Stavanger) | Wrobel, Stanislaw (University of Stavanger) | Hamon, Gérald (Total E&P)
Low salinity water injection in sandstone is an emerging technology just on the verge of being implemented full field in the UK and in Alaska, USA. Laboratory studies are important for providing relevant and well interpreted data before performing the field trial. However, laboratory investigations show varying results on low salinity EOR, most probably because of a limited understanding of the nature of the process. Recently we have published a "Smart Water" EOR mechanism where pH changes at the rock surface is inducing the wettability alteration, improving positive capillary forces and microscopic sweep efficiency. Researchers have experienced rather poor low salinity EOR effects from 17 different sandstone outcrops from the USA.
In this work we have investigated 6 of the same 17 outcrops, and according to our chemical understanding, some factors are more important for observing LS EOR effects in sandstone. It is the increase in pH, ?pH, obtained when the high salinity (HS) formation water is displaced by the low salinity (LS) injection water, and it is the initial pH and the amount of active cations (Ca2+) in the formation water that are related to the initial wetting.
We have established a link between the poor low salinity EOR effect from all 6 outcrops and the corresponding pH change observed when switching from high salinity to low salinity injection water. The presence of different types of minerals such as clay, feldspars and anhydrite will influence the pH change, and must be taken into account. Additionally, we have seen that the formation water composition has strong influence on the low salinity EOR effect. Using a formation water with salinity like seawater (FW1 ~35 000 ppm) showed only a minor tertiary low salinity EOR effect, 0.74 %OOIP, corresponding to a low pH gradient of 0.5. While experiments using a high salinity formation water (FW2 ~100 000 ppm) showed a 5 % OOIP recovery, corresponding to a larger pH gradient of 2.0.
The results observed are in agreement with the suggested chemical mechanism for the low salinity EOR effect, confirming that it is the pH gradient that triggers the low salinity EOR effect. In addition, the pH screening test used in this work proved once again to be a reliable tool to evaluate the low salinity EOR potential.
Kuznetsov, Oleksandr (Baker Hughes) | Mazyar, Oleg (Baker Hughes) | Agrawal, Devesh (Baker Hughes) | Suresh, Radhika (Baker Hughes) | Feng, Xianhua (Baker Hughes) | Behles, Jackie (Baker Hughes) | Khabashesku, Valery (Baker Hughes)
Oil sand ore flotation is a primary method of bitumen recovery from mined Athabasca tar sands. In bitumen flotation, suspended biwettable ore fines, such as clays, tend to migrate to oil-water interfaces, creating slime coating on liberated bitumen droplets. Slime coating significantly reduces the efficiency of the flotation process and overall oil recovery. Ultra-dispersed hydrophilic silica nanoparticles were found to stabilize biwettable ore fines in an aqueous phase by adsorbing onto fines surfaces, even at concentrations as low as 50 ppm. As a result, fine solids move away from oil/water interfaces, reducing the slime coating and increasing bitumen recovery during flotation of low-grade ore by more than 5%. The addition of nanoparticles has no negative effect on froth quality or oil, water and solid separation in naphthenic and paraffinic froth treatment processes. Detailed molecular dynamics (MD) simulations revealed mechanisms that improve bitumen liberation from mined oil sands in a flotation process. The studies demonstrated that colloidal nanoparticles affect many stages of the bitumen extraction process from bitumen separation to clay wettability alteration.