XU, Ke (The University of Texas at Austin) | Zhu, Peixi (The University of Texas at Austin) | Tatiana, Colon (Polytechnic University of Puerto Rico) | Huh, Chun (The University of Texas at Austin) | Balhoff, Matthew (The University of Texas at Austin)
Injecting oil-in-water (O/W) emulsions stabilized with nanoparticles or surfactants is a promising option for enhanced oil recovery (EOR) in harsh-condition reservoirs. Stability and rheology of flowing emulsion in porous media are key factors for the effectiveness of the EOR method. The objective of this study is to use microfluidics to (1) quantitatively evaluate the synergistic effect of surfactants and nanoparticles on emulsion's dynamic stability and how nanoparticles affects the emulsion properties, and (2) investigate how emulsion properties affect the sweep performance in emulsion flooding.
A microfluidic device with well-defined channel geometry of a high-permeability pathway and multiple parallel low-permeability pathways was created to represent a fracture – matrix dual-permeability system. Measurement of droplets’ coalescence frequency during flow is used to quantify the dynamic stability of emulsions. A nanoparticle aqueous suspension (2 wt%) shows excellent ability to stabilize macro-emulsion when mixed with trace amount of surfactant (0.05 wt%), revealing a synergic effect between nanoparticles and surfactant.
For a stable emulsion, it was observed that flowing emulsion droplets compress each other and then block the high-permeability pathway at a throat structure, which forces the wetting phase into low-permeability pathways. Droplet size shows little correlation with this blocking effect. Water content was observed much higher in the low-permeability pathways than in the high-permeability pathway, indicating different emulsion texture and viscosity in channels of different sizes. Consequently, the assumption of bulk emulsion viscosity in the porous medium is not applicable in the description and modeling of emulsion flooding process.
Flow of emulsions stabilized by the nanoparticle-surfactant synergy shows droplet packing mode different from those stabilized by surfactant only at high local oil saturation region, which is attributed to the interaction among nanoparticles in the thin liquid film between neighboring oil-water interfaces. This effect is believed to be an important contributing mechanism for sweep efficiency attainable from nanoparticle-stabilized emulsion EOR process.
It is generally assumed that while the presence of foam reduces the mobility of the gas phase, it does not alter the mobility of the liquid phase. Here, the effect of surfactant type and concentration on the behavior of nitrogen foam flow in porous media is investigated by simultaneous injection of gas and surfactant into Bentheimer sandstone cores. Different surfactant types, viz., anionic alpha-olefin-sulfonate (AOS) and zwitterionic Betaine with different surfactant concentrations from critical-micelle-concentration (CMC) to higher concentration are used in this study. The foam strength is quantified by measuring the pressure drop in different sections of the core. The liquid saturation is measured by analyzing the X-ray images obtained in a medical CT-scanner.
It is shown that the connate water saturation is reduced by increasing the surfactant concentration, and therefore the relative permeability relation for the aqueous phase should be modified when fitting the data to the foam models. It is observed that it is not possible to fit one monotonic liquid relative permeability curve to all the data points, obtained with different surfactant type and concentration in one rock type. Moreover, increasing AOS concentration above a certain value does not have a significant effect on the mobility reduction of the gas phase; however it modifies the liquid relative permeability. These results indicate that the water relative permeability measured in absence of surfactant should not be used to model the flow of foam in porous media, as it can lead to erroneous calculations of the liquid saturation.
Jin, Luchao (University of Oklahoma) | Budhathoki, Mahesh (University of Oklahoma) | Jamili, Ahmad (University of Oklahoma) | Li, Zhitao (The University of Texas at Austin) | Luo, Haishan (The University of Texas at Austin) | Delshad, Mojdeh (The University of Texas at Austin) | Shiau, Ben (University of Oklahoma) | Harwell, Jeffrey H. (University of Oklahoma)
The surfactant screening process to develop an optimum formulation under reservoir conditions is typically time consuming and expensive. Theories and correlations like HLB, R-ratio and packing parameters have been developed. But none of them can quantitatively consider both the effect of oil type, salinity, hardness and temperature, and model microemulsion phase behavior.
This paper uses the physics based Hydrophilic Lipophilic Difference (HLD) Net Average Curvature (NAC) model, and comprehensively demonstrated its capabilities in predicting the optimum formulation and microemulsion phase behavior based on the ambient conditions and surfactant structures. By using HLD equation and quantitatively characterized parameters, four optimum surfactant formulations are designed for target reservoir with high accuracy compared to experimental results. The microemulsion phase behavior is further predicted, and well matched the measured equilibrium interfacial tension. Its predictability is then reinforced by comparing to the empirical Hand's rule phase behavior model. Surfactant flooding sandpack laboratory tests are also interpreted by UTCHEM chemical flooding simulator coupled with the HLD-NAC phase behavior model.
The results indicate the significance of HLD-NAC equation of state in not only shorten the surfactant screening processes for formulators, but also predicting microemulsion phase behavior based on surfactant structure. A compositional reservoir simulator with such an equation of state will increase its predictability and hence help with the design of surfactant formulation.
Favorable microemulsion rheology is required for achieving low surfactant retention and economic viability of chemical EOR. Co-solvents play a pivotal role in obtaining favorable microemulsion rheology as well as many other aspects of chemical EOR. We measured the partitioning of co-solvents between phases to better understand their behavior and how to select the best co-solvent for chemical EOR. There is an optimal co-solvent partition coefficient for microemulsion systems. Commercial co-solvents used for chemical EOR are actually mixtures of different components. We used HPLC to measure the partitioning of the constitutive components of phenol ethoxylate co-solvents between oil and water phases and between microemulsion and excess oil and water phases. These measurements show that the components partition independently and the partitioning of individual components is often different from the average. The co-solvent partition coefficients between oil and water were systematically evaluated as functions of the number of ethylene oxide groups, number of propylene oxide groups, temperature, salinity, and the equivalent alkane carbon number (EACN) of the oil. Novel alkoxylate co-solvents were also evaluated for chemical EOR. The novel alkoxylate co-solvents can be more effectively tailored to match the characteristics of different crude oils. Coreflood experiments were conducted to investigate co-solvent transport and retention. Co-solvents were identified that showed excellent performance and low retention.
Zhu, Youyi (State Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC) | Fan, Jian (State Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC) | Liu, Xiaoxia (State Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC) | Li, Jianguo (State Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC)
Chemical flooding technology is one of the effective enhanced oil recovery (EOR) methods for high water cut sandstone reservoirs with either medium and/or high permeability. Because of the small pore throat radius in the pore medium of low permeability reservoir, high molecular weight polymers cannot be injected in the low permeability reservoir. Therefore, many traditional chemical floodings (such as polymer flooding, alkali-surfactant-polymer (ASP) flooding and surfactant-polymer (SP) flooding) cannot be effectively applied in this case. Small-molecule viscoelastic surfactant (VES) has special rheological properties in porous medium. It showed both viscosified function and reduction of oil/water interfacial tension (IFT) performances under certain conditions, thereby providing the possibility of IOR/EOR potential application in low permeability reservoirs.
Most of reservoirs in Jilin Oilfield belong to low permeability reservoirs with permeability of around 50 mD in average. The recovery percent of reserves in Fuyu was only 23% by water flooding with water cut as high as 93%. A candidate EOR technique with chemical flooding has been proposed. Studies on VES flooding EOR methods targeting this reservoir condition were conducted. The rheological property, IFT property, viscosifying ability of VES and core flooding experiments of VES system were studied.
From VES screening experiment, a type of zwitterionic betaine surfactant with long carbon chain was selected. It showed viscosifying behavior, shear thinning property and low IFT performances at reservoir conditions. VES of EAB solutions showed a good viscosifying action at low surfactant concentration. Moreover, based on its shear thinning property under the wide shear rate conditions, VES exhibited a good injectivity performance. IFT between crude oil and formation water with EAB was 10-3-10-2 mN/m order of magnitudes. The results could be obtained at the concentration ranges of surfactants from 0.1wt% to 0.4wt%. Ultralow IFT (10-3 mN/m order of magnitudes) could be obtained in the presence of co-surfactants or alkalis (such as sodium carbonate). Core flooding experiments of VES flooding showed that the incremental oil recovery factors could reach up to 13%-17% over conventional water flooding at Fuyu reservoir conditions. Test results indicated that VES flooding might become a promise alternative EOR method for low permeability reservoir after water flooding.
In contrast to the complexity of ASP/SP combination system, VES flooding could avoid chromatographic effects in the reservoir based on their simple formula (single surfactant compound). This new chemical flooding technique might have a great potential for EOR application in the low permeability reservoirs.
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.
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.
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.
Davidson, Andrew (Chevron Energy Technology Company) | Nizamidin, Nabijan (Chevron Energy Technology Company) | Alexis, Dennis (Chevron Energy Technology Company) | Kim, Do Hoon (Chevron Energy Technology Company) | Unomah, Michael (Chevron Energy Technology Company) | Malik, Taimur (Chevron Energy Technology Company) | Dwarakanath, Varadarajan
Low microemulsion viscosity is critical for the success of chemical EOR. Typical microemulsion viscosities are measured using a rheometer and are considered to be static measurements. Given that microemulsions have a propensity to show non-Newtonian behavior, static viscosity measurements are not scalable to dynamic viscosities observed in cores and hence difficult to scale-up to field designs using simulations. We present a technique to measure dynamic microemulsion viscosity using a modified two-phase steady state relative permeability setup. Such dynamic viscosities provide a more practical feel for microemulsion viscosity under reservoir conditions in the pores and allow for selection of low microemulsion viscosity formulations. A two-phase steady state relative permeability setup was used with continuous co-injection of oil and surfactant. A glass filled sand pack was used as a surrogate core and the injection fluids were allowed to equilibrate into the appropriate phases as determined by the phase behavior. For the rapidly equilibrating and low viscosity Winsor Type III formulations three phases are clearly observed in the sand packs. Using the phase cuts in the sand pack/effluent and the known oil and water viscosities, we can estimate the microemulsion viscosity. Both low and high viscosity formulations were tested in corefloods and oil recovery measured to illustrate the importance of low viscosity microemulsions for oil recovery. As expected, the low viscosity microemulsions correlated with higher oil recovery. In addition, the equilibration times to reach Winsor Type III microemulsions were also linked to better oil recovery. For the well behaved formulations that equilibrated in less than 2 days the static microemulsion viscosity correlated well with the dynamic viscosity. The modified steady state relative permeability setup can accurately estimate microemulsion viscosity and allow for better screening of surfactant formulations identified for field flooding. The dynamic microemulsion viscosities can also provide inputs for numerical simulation and better predict microemulsion behavior in the subsurface during field surfactant floods.
Sharma, Himanshu (The University of Texas at Austin) | Lu, Jun (The University of Texas at Austin) | Weerasooriya, Upali P. (The University of Texas at Austin) | Pope, Gary A. (The University of Texas at Austin) | Mohanty, Kishore K. (The University of Texas at Austin)
Recent studies on the use of ammonia as an alkali for performing alkali-surfactant-polymer (ASP) floods have shed light on its advantages over conventional alkalis such as lower alkali requirements, ease of transportation and storage. This study is aimed towards understanding surfactant adsorption in sandstone and carbonate rocks in the presence of ammonia. Zeta potential measurements were performed to characterize Bandera brown sandstone and Silurian dolomite surfaces in the presence of ammonia and sodium carbonate. A series of experiments were performed with and without ammonia such as static surfactant adsorption experiments on crushed Bandera brown sandstone and Silurian dolomite rocks, single phase surfactant transport experiments in sandstone and carbonate cores, surfactant phase behavior to identify an ultra-low interfacial tension (IFT) surfactant formulation, and oil recovery coreflood experiments using these surfactant formulations. Zeta potential measurements showed a reduction in zeta potential of Bandera brown and Silurian dolomite by adding ammonia to increase the pH. Surfactant adsorption experiments showed that ammonia was able to reduce the adsorption on sandstones, but not much difference was observed for carbonates. The ultra-low IFT surfactant formulations developed with and without ammonia showed very similar phase behavior. High oil recoveries and very low surfactant retentions were observed in the oil recovery experiments performed in sandstones.