Although geochemical reactions are the fundamental basis of the alkaline/surfactant/polymer (ASP) flooding, their importance is commonly overlooked and not fully assessed. Common assumptions made when modeling geochemical reactions in ASP floods include: 1) ideal solution (i.e., using molalities rather than ion activities) for the water and aqueous geochemical species 2) limiting the number of reactions (i.e., oil/alkali and alkali consumptions) rather than including the entire thermodynamically-equilibrated system 3) ignoring the effect of temperature and pressure on reactions 4) local equilibrium ignoring the kinetics. To the best of our knowledge, the significance of these assumptions has never been discussed in the literature. In this paper we investigate the importance of geochemical reactions during alkaline/surfactant/polymer floods using a comprehensive tool in the sense of surfactant/soap phase behavior as well as geochemistry.
We coupled the United States Geological Survey (USGS) state-of-the-art geochemical tool, with 3D flow and transport chemical flooding module of UTCHEM. This geochemical module includes several thermodynamic databases with various geochemical reactions, such as ion speciation by applying several ion-association aqueous models, mineral, solid-solution, surface-complexation, and ion-exchange reaction. It has capabilities of saturation index calculation, reversible and irreversible reactions, kinetic reaction, mixing solutions, inverse modeling and includes impacts of temperature and pressure on reaction constants and solubility products. The chemical flood simulator has a three phase (water, oil, microemulsion) phase behavior package for the mixture of surfactant/soap, oil, and water as a function of surfactant/soap, salinity, temperature, and co-solvent concentration. Hence, the coupled software package provides a comprehensive tool to assess the significance of geochemical assumptions typically imposed in modeling ASP floods. Moreover, this integrated tool enables modeling of variations in mineralogy present in reservoir rocks. We parallelized the geochemistry module of this coupled simulator for large-scale reservoir simulations.
Our simulation results show that the assumption of ideal solution overestimates ASP oil recovery. Assuming only a subset of reactions for a coupled system is not recommended, particularly when a large number of geochemical species is involved, as is the case in realistic applications of ASP. Reservoir pressure has a negligible effect but temperature has a significant impact on geochemical calculations. Although mineral reaction kinetics is largely a function of the temperature and in-situ water composition, some general conclusions can be drawn as follows: to a good approximation, minerals with slow rate kinetic reaction (e.g., quartz) can be excluded when modeling ASP laboratory floods. However, minerals with fast rate kinetic reactions (e.g., calcite) must be included when modeling lab results. On the other hand, in modeling field-scale applications, local equilibrium assumption (LEA) can be applied for fast rate kinetic minerals, whereas kinetics should be used for slow rate kinetic minerals.
Rohilla, Neeraj (TIORCO, a Nalco Champion Company) | Ravikiran, Ravi (Stepan Company) | Carlisle, Charlie T. (Chemical Tracers Inc.) | Jones, Nick (University of Wyoming) | Davis, Marron B. (Sunshine Valley Petroleum Corporation) | Finch, Kenneth B. H. (TIORCO, a Nalco Champion Company)
Sandstone reservoirs containing significant amount of clays (30-40 wt%) with moderate permeability (20-50 mD) provide a unique challenge to surfactant based enhanced oil recovery (EOR) processes. A critical risk factor for these types of reservoirs is adsorption of surfactants due to greater surface area attributed to clays. Clays also have high cation exchange capacity (CEC) and can release significant amounts of di-valents that lead to increased retention of the surfactant. These factors could adversely affect the economics of a flood.
We present a case study where a robust formulation was designed and tested in lab/field for a reservoir located in Wyoming, USA and contains up to 35-40 wt% clays (predominately Kaolinite and Illite). The residual oil saturation is high (Sor=0.4) while the permeability of the formation is between 20-50 mD. The reservoir has been waterflooded historically with low salinity water which has led to formation permeability damage. Due to high levels of clays, adsorption of the surfactant on the rock surface was determined to be between 3-4 mg/g rock by static adsorption tests.
This publication demonstrates how the following challenges have been successfully addressed in the lab as well as in the field in the form of single well chemical tracer test (SWCTT).
Designed a robust alkaline-surfactant-polymer (ASP) formulation that showed ultra-low interfacial tension (IFT) values and aqueous solubility remains soluble in the aqueous solution over a broad range of salinity. Mitigated surfactant adsorption issues to make the cEOR solution economic. A sacrificial agent was identified that acted synergistically with alkali and also did not alter the optimum salinity of the formulation. Performed restored state core analysis using the available damaged core material. The main challenge being restoration of the coreplugs to current reservoir conditions for coreflood experiment without causing additional formation damage due to injection of low salinity formation brine. Designed a flood that utilized a pre-flush to provide a favorable salinity gradient and to inject sacrificial agent ahead of the surfactant front. Performed polymer screening to select right molecular weight of polymer so that the right balance of mobility control and injectivity in the reservoir can be obtained.
Designed a robust alkaline-surfactant-polymer (ASP) formulation that showed ultra-low interfacial tension (IFT) values and aqueous solubility remains soluble in the aqueous solution over a broad range of salinity.
Mitigated surfactant adsorption issues to make the cEOR solution economic. A sacrificial agent was identified that acted synergistically with alkali and also did not alter the optimum salinity of the formulation.
Performed restored state core analysis using the available damaged core material. The main challenge being restoration of the coreplugs to current reservoir conditions for coreflood experiment without causing additional formation damage due to injection of low salinity formation brine.
Designed a flood that utilized a pre-flush to provide a favorable salinity gradient and to inject sacrificial agent ahead of the surfactant front.
Performed polymer screening to select right molecular weight of polymer so that the right balance of mobility control and injectivity in the reservoir can be obtained.
Alkaline-surfactant-polymer (ASP) flooding of a viscous oil (100 cp) is studied here in a two-dimensional (2D) sand pack. An ASP formulation was developed by studying the phase behavior of the oil with several alkaline-surfactant formulations. The effectiveness of the ASP formulation was validated in a 1D sand pack by conducting a water flood followed by a stable ASP flood. Reservoir sand was then packed into a 2D square steel cell similar to a quarter five-spot pattern. Several ASP floods were then conducted in this 2D cell to study both the displacement and sweep efficiency of ASP floods. First, the polymer concentration was varied to find an optimum polymer concentration. Then the waterflood extent was varied (0–1 PV) after which the ASP flood was initiated. The oil recovery, oil cut, effluent concentration and pressure drop were monitored during the floods. The tertiary ASP flood was very effective in 1D and validated the ASP formulation. The 2D tertiary ASP flood also recovered most of the oil (~98% of OOIP) when the ASP slug viscosity exceeded the oil viscosity, but the pressure gradients were high at ~ 1ft/d injection. When the ASP slug viscosity was lowered to ~1/3 of oil viscosity, oil recovery dropped slightly to 90% OOIP. However, it also decreased the pressure gradient 5 times, which would give good flow rates in the field conditions. As the extent of waterflood preceding ASP got shorter, the oil was recovered faster (for the same pore volumes injected), but the pressure gradient was higher for the ASP flood than the water flood. The ultimate recovery was independent of the extent of waterflood.
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.
Microemulsion properties significantly impact any EOR process that relies on surfactants or soaps to generate ultralow interfacial tension to displace trapped oil. Unfavorable microemulsion viscosity can lead to high chemical retention, low oil recovery, and overall unfavorable performance across all modes. Controlling microemulsion properties is important in conventional approaches like surfactant-polymer (SP) and alkaline-surfactant-polymer (ASP) flooding, in addition to new applications like gravity stable displacements, spontaneous imbibition in fractured carbonates and unstable floods of viscous oil. Despite the central importance, microemulsion viscosity and rheology remain poorly understood.
This paper describes the results of an extensive experimental microemulsion study. We evaluated the effect of polymer on microemulsion viscosity in different microemulsion phase types (i.e. oil in water, bi-continuous, water in oil emulsions). We measured microemulsion viscosities across a broad salinity range for several crudes from light (API >30°) to heavy oils (API<14°) and observed Newtonian rheology for all phase types. The effect of cosolvents on microemulsion viscosity was also evaluated. Finally, we evaluated microemulsions with and without alkali to help understand potential differences between ASP and SP microemulsions.
We include many observations consistent with earlier literature using recently developed surfactants and report the microemulsion viscosity details for many high performance surfactant formulations across a wide range of conditions. We have also describe several observations, including polymer decreasing the required time to achieve equilibrium in microemulsion pipettes and the qualitative change in microemulsion behavior with and without polymer in Windsor Type III microemulsions.
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.
Dwarakanath, Varadarajan (Chevron) | Dean, Robert M. (Chevron) | Slaughter, Will (Chevron) | Alexis, Dennis (Chevron) | Espinosa, David (Chevron) | Kim, Do Hoon (Chevron) | Lee, Vincent (Chevron) | Malik, Taimur (Chevron) | Winslow, Greg (Chevron) | Jackson, Adam C. (Chevron) | Thach, Sophany (Chevron)
Polymer flooding by liquid polymers is an attractive technology for rapid deployment in remote locations. Liquid polymers are typically oil external emulsions with included surfactant inversion packages to allow for rapid polymer hydration. During polymer injection, a small amount of oil is typically co-injected with the polymer. The accumulation of the emulsion oil near the wellbore during continuous polymer injection will reduce near wellbore permeability. The objective of this paper is to evaluate the long-term effect of liquid polymer use on polymer injectivity. We also present a method to remediate the near well damage induced by the emulsion oil using a remediation surfactant that selectively solubilizes and removes the near wellbore oil accumulation. We evaluated several liquid polymers using a combination of rheology measurement, filtration ratio testing and long-term injection coreflood experiments. The change in polymer injectivity was quantified in surrogate core after multiple pore volumes of liquid polymer injection. Promising polymers were further evaluated in both clean and oil-saturated cores. In addition, phase behavior experiments and corefloods were conducted to develop a surfactant solution to remediate the damage induced by oil accumulation. Permeability reduction due to long term liquid polymer injection was quantified in cores with varying permeabilities. The critical permeability where no damage was observed was identified for promising liquid polymers. A surfactant formulation tailored for one of the liquid polymers improved injectivity three- to five-fold and confirms our hypothesis of permeability reduction due to emulsion oil accumulation. Such information can be used to better select appropriate polymers for EOR in areas where powder polymer use may not be feasible.
The application of surfactants to improve oil recovery in conventional reservoirs via wettability alteration and enhancement of spontaneous imbibition has been extensively studied in the literature. However, little work has been performed yet to investigate the interaction of these surfactants with ultra-tight oil-rich shale reservoirs such as Wolfcamp shale. The use of horizontal drilling and massive multistage hydraulic fracturing has made primary oil recovery from these ultra-tight oil-rich shale reservoirs possible. With declining production from existing shale wells, it is essential to explore potential "beyond primary" strategies in shale oil development. This paper analyzes the potential of surfactants in altering wettability and improving the process of spontaneous imbibition in oil rich shales demonstrating nanodarcy range permeability, relevant to stimulation and "beyond primary" chemical EOR applications in shales.
Novel proprietary surfactant blends along with traditional nonionic surfactants were investigated in this study using Wolfcamp shale core samples exhibiting nanodarcy permeability. X-ray diffraction analysis was performed which indicated that Wolfcamp shale has mixed mineralogy, with quartz, calcite, and dolomite acting as the major minerals in varying proportions depending on the interval depth. Contact angle and interfacial tension measurements were performed at reservoir temperature to identify the state of native wettability and the impact of surfactants in altering wettability. Thereafter, spontaneous imbibition experiments were performed using 3D computed tomography methods to understand the improvement in the magnitude of imbibition penetration due to surfactant addition. Contact angle and spontaneous imbibition experiments showed that Wolfcamp shale is intermediate-wet and surfactants have the potential to alter the native wettability to a preferentially water-wet state and improve oil recovery due to enhanced spontaneous imbibition.
Surfactants which altered the wettability significantly, but lowered the interfacial tension only slightly showed the highest oil recoveries due to the creation of strong capillary driven forces directly responsible for effective spontaneous imbibition. The potential of surfactants in altering wettability and improving oil recovery via enhanced spontaneous imbibition in ultra-tight oil-rich shales was verified in this study. The effectiveness of traditional nonionic surfactants in altering wettability and improving oil recovery was found to be comparable to that of novel, more expensive proprietary surfactant blends, and hence, the traditional nonionic surfactants provide a cost effective option for stimulation and EOR applications in Wolfcamp shale. Overall, this paper presents the theory behind surfactant interaction with ultra-tight shales and provides experimental results to validate the viability of surfactant induced improved oil recovery in shales.
In the case of surfactant EOR, an optimum formulation of surfactant has to be injected in the reservoir. This so-called optimum formulation corresponds to a minimum in the interfacial tension and a maximum in oil recovery and may be obtained with an appropriate balance of the hydrophobic and hydrophilic affinities of the surfactant. Salinity—scan tests are generally used to screen phase behavior of surfactant formulations before conducting time-consuming coreflood tests. The objective of this study was to develop a high-throughput dynamic microfluidic tensiometer, with the aim of studying interfacial phenomena between EOR injected formulations and crude oils and of optimizing chemical EOR processes for pilot or field applications.
We have selected a method based on the Rayleigh-Plateau instability and the analysis of the droplets to jetting transition in a coaxial flow of two fluids. In fact, in coaxial flows, the transition between a droplet and a jetting regime depends on the velocities of each phase, the viscosity ratio, the confinement and the interfacial tension (IFT). As the three first parameters are known, the dynamic interfacial tension can be calculated. This microfluidic device has been specifically designed to support high temperatures (up to 150°C), high pressures (up to 150 bars) and is compatible with complex fluids such as crude oils and solutions of surfactants and polymers.
The method was first developed and validated on a microfluidic device on model fluids at ambient temperature and atmospheric pressure for IFTs higher than 1 mN/m. It was then successfully applied for the measurement of IFTs over more than four decades. Measurements were also performed with a crude oil and a typical surfactant formulation. The validation of the HP/HT assembly, which has been designed with the aim to work in reservoir conditions, is currently under progress. By using this tensiometer, it would be quite easy to perform in short time numerous salinity scans on real systems in order to get the evolution of IFT and determine the optimal salinity S*.
Li, Yuxiang (The University of Texas at Austin) | Lu, Jun (The University of Texas at Austin) | Churchwell, Lauren (The University of Texas at Austin) | Tagavifar, Mohsen (The University of Texas at Austin) | Weerasooriya, Upali (The University of Texas at Austin) | Pope, Gary A. (The University of Texas at Austin)
Primary and secondary oil recovery from naturally fractured carbonate reservoirs with an oil-wet matrix is very low. Enhanced oil recovery from these reservoirs using surfactants to alter the wettability and reduce the interfacial tension have been extensively studied for many years, but there are still many questions about the process mechanisms, surfactant selection and testing, experimental design and most importantly how to scale up the lab results to the field. We have conducted a series of imbibition experiments using cores with different vertical and horizontal dimensions to better understand how to scale up the process. There was a particular need to perform experiments with larger horizontal dimensions since almost all previous experiments have been done in cores with a small diameter, typically 3.8 cm. We adapted and modified the experimental method used for traditional static imbibition experiments by flushing out fluids surrounding the cores periodically to better estimate the oil recovery, including the significant amount of oil produced as an emulsion. We used microemulsion phase behavior tests to develop high performance surfactant formulations for the oils used in this study. These surfactants gave ultra-low IFT at optimum salinity and good aqueous stability. Although we used ultra-low IFT formulations for most of the experiments, we also performed tests at higher IFT for comparison. Even for the higher IFT experiments, the capillary pressure is very small compared to gravity and viscous pressure gradients. We also developed a simple analytical model to predict the oil recovery as a function of vertical and horizontal fracture spacing, rock properties and fluid properties. The model and experimental data are in good agreement considering the many simplifications made to derive the model. The scaling implied by the model is significantly different than traditional scaling groups in the literature.