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.
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.
Hou, Binchi (Research Institute of Shaanxi Yanchang Petroleum (Group) CO., LTD.) | Liu, Hongliang (China Petroleum Logging TuHa Business Division) | Bian, Huiyuan (Xi'an University of Science and Technology) | Wang, Chengrong (China Petroleum Logging TuHa Business Division) | Xie, Ronghua (Daqing Oilfield CO.LTD., PetroChina) | Li, Kewen (China University of Geosciences(Beijing)/Stanford University)
Capillary pressure and resistivity in porous rocks are both functions of wetting phase saturation. Theoretically, there should be a relationship between the two parameters. However, few studies have been made regarding this issue. Capillary pressure may be neglected in high permeability reservoirs but not in low permeability reservoirs. It is more difficult to measure capillary pressure than resistivity. It would be useful to infer capillary pressure from resistivity well logging data if a reliable relationship between capillary pressure and resistivity can be found. To confirm the previous study of a power law correlation between capillary pressure and resistivity index and develop a mathematical model with a better accuracy, a series of experiments for simultaneously measuring gas-water capillary pressure and resistivity data at a room temperature in 16 core samples from 2 wells in an oil reservoir were conducted. The permeability of the core samples ranged from 9 to 974 md. The gas-water capillary pressure data were measured with confining pressures using a semi-porous plate technique. We developed the specific experimental apparatus to measure gas-water capillary pressure and resistivity simultaneously. The results demonstrated that the previous power law model correlating capillary pressure and resistivity works well in many cases studied. A more general relationship between the exponent of the power law model and the rock permeability was developed and verified using the experimental data.
Low-salinity waterflooding has been portrayed as an effective enhanced-oil recovery technology. Despite compelling laboratory and field evidence of its potential, the underlying mechanisms still remain controversial. In this study, the enhanced-oil recovery mechanisms are investigated considering a distinct interfacial effect, i.e. water-crude oil interfacial viscoelasticity, through analysis of capillary hysteresis. An experimental setup with an oil-wet and a water-wet media on each end face of the core sample was utilized to capture capillary and rock electrical properties hysteresis. Moreover, new improvements over the traditional quasi-static porous plate method were implemented to accelerate measurements. Two experiments were conducted on Minnelusa formation rock samples and TC crude oil, at low temperature (30 °C) and without any significant aging as to minimize wettability alteration. Two core plugs were flooded with high-salinity and low-salinity brines, separately. It is found that the dynamic-static method with a ceramic disk, i.e. a combination of continuous injection in drainage and stepwise quasi-static method in imbibition on short 1" long core samples, allows one to capture the correct envelopes of the capillary pressure curves and save ~ 30% of the total time; a thin membrane is anticipated to save ~90% with respect to traditional quasi-static porous plate method. The capillary hysteresis experiments at low temperature prove that low-salinity brine is able to suppress capillary hysteresis. This is attributed to the formation of a more visco-elastic brine-crude oil interface upon exposure to low-salinity brine, leading to a more continuous oil phase. In addition, we show that wettability plays an essential role on electrical resistivity and the more oil-wet, the more hysteresis occurs, namely that resistivity values in imbibition are higher than those in drainage. The findings in this paper demonstrate that low-salinity waterflooding can still increase oil recovery even in the absence of wettability alteration.
Production from tight formation resources leads the growth in U.S. crude oil production. Compared with chemical flooding and water flooding, gas injection is a promising EOR approach in shale reservoirs. A limited number of experimental studies concerning gas flooding in the literature focus on unconventional plays. This study is a laboratory investigation of gas flooding to recover light crude oil from nano-permeable shale reservoirs.
In this work, the N2 flooding process was applied to Eagle Ford core plugs saturated with dead oil. To investigate the effects of flooding time and injection pressure on the recovery factor, two groups of core-flood tests were performed. In group one, flooding time ranged from 1 to 5 days in increments of 1 day; in the other group, the injection pressure ranged from 1,000 psi to 5,000 psi in increments of 1,000 psi. The experimental setup was monitored using X-ray CT that helped to visualize phase flow and estimate the recovery efficiency during the test.
The potential of N2 flooding for improving oil recovery from shale core plugs was examined, and the recovery factor (RF) of each case was presented. The results from group one showed that more oil was produced with a longer flooding time. However, the incremental RF decreased with the increase of flooding time. The oil recovery was significant at the initial period of the recovery process, and a longer flooding time had less effect on extracting more oil. With flooding time constant in 1-day, the results from the second group indicated that RF increased with injection pressure, especially rising pressure, from 1,000 psi to 2,000 psi. The gas breakthrough time became shorter with the increase of injection pressure. The analysis of the CT number showed that the oil recovery process mainly occurred before the gas breakthrough. Once a fluid flow path was established, the injected gas flowed through the limited communication channels; thus, no extra oil could be extracted without increasing the injection pressure. This experimental study illustrates that gas flooding has liquid oil production potential in shale reservoirs.
This is the final installment in a series of three papers examining iron mineralogy and its effect on surfactant adsorption in reservoir and outcrop rock samples. The goal of these studies is to establish best practices for obtaining surfactant adsorption values representative of those in a reduced oil reservoir, despite performing experiments in an oxidizing laboratory atmosphere.
This article follows two others examining the abundance and form of iron in the reservoir and in core samples (Part I:
Surfactant retention is a leading uncertainty in economic forecasting of chemical EOR, in large part due to the order-of-magnitude effects of artifacts such as improper core preservation. The industry standard is to (a) limit atmospheric contact of cores to the extent feasible, and (b) when necessary, reduce oxidized cores using strong reducing agents such as sodium dithionite, along with buffering and chelating agents such as sodium bicarbonate and EDTA or sodium citrate. However few studies have been performed to determine whether such invasive treatments are necessary, or what unintended effects the use of such reactive chemicals may have.
The most striking conclusion from these studies is the lack of clear evidence of any advantage of electrochemical reduction versus a simpler treatment with chelators such as sodium citrate or EDTA.
While treatment with a citrate-bicarbonate-dithionite solution does indeed lower adsorption several-fold further, solutions of either sodium bicarbonate or EDTA are at least as effective, and sodium citrate is almost as effective. These non-reductive treatments remove small amounts (~0.1% – ~0.2% of rock mass) of Fe and Al, and fines are invariably apparent in treatment fluids, both of which suggest removal of small amounts of trivalent Fe/Al colloids.
While these results suggest that non-reductive means may be used to remove artifacts introduced by core oxidation, they come with an important caveat: even rinsing with a brine solution can result in significant alteration of mineralogy. The use of chelating agents will invariably result in dissolution of any soluble minerals present such as gypsum or anhydrite, which can be an important contributor to surfactant (in particular ABS) consumption.
In cases where iron removal is necessary due to polymer degradation issues, PIPES buffer is proposed for use as an alternative to bicarbonate, the latter having a greater tendency for ligand formation. The combination of borohydride and bisulfite is suggested as an alternative to dithionite as a reducing agent, resulting in more complete iron removal under some conditions, and anecdotally less tendency for polymer degradation upon subsequent oxidation, though both of these claims should be verified.