The Green River, Utah holds the world's greatest oil shale resources. However, the hydrocarbon, which is namely kerogen, extraction from shales is limited due to environmental and technical challenges. In this study, we investigated the effectiveness of the combustion process for shale oil extraction. Samples collected from the Green River formation were first characterized by X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Then, series of dry combustion tests were conducted at different heating rates and wet combustion tests by water addition. The combustion efficiency was enhanced by mixing oil shale samples with an iron based catalyst. The effectiveness of dry, wet, and catalyst added combustion processes was examined by the thermal decomposition temperature of kerogen. Because the conventional oil shale extraction methods are pyrolysis (retorting) and steaming, the same experiments were conducted also under nitrogen injection to mimic retorting. It has been observed that the combustion process is a more efficient method for the extraction of kerogen from oil shale than the conventional techniques. The addition of water and catalyst to combustion has been found to lower the required temperature for kerogen decomposition for lower heating rate. This study provides insight for the optimization of the thermal methods for the kerogen extraction.
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.
Achieving maximum oil recovery utilizing CO2 has limitations when operating at, or very close, to the Minimum Miscibility Pressure (MMP) of the CO2 in the oil. A modular source of CO2 would allow Enhanced Oil Recovery (EOR) flooding of "stranded" and shallow reservoirs. Unfortunately, modular sources of CO2 production often include CO and N2 mixed with the CO2. Thus, testing for EOR application of a mixed gas-containing CO2, N2, and CO was initiated.
Bench scale testing using Rising Bubble Apparatus (RBA), Slim Tubes, and linear core flood have been conducted on oils ranging from 16-42° gravities having viscosities of 0.5-280 cp. All tests were conducted at reservoir temperatures and pressures. CO, being a strong reducing agent, was further tested on reservoir rock containing swelling clays with hydrated ferric hydroxides. Due to the apparent reduction of the ferric hydroxide, and the liberation of its water of hydration, an increase in matrix permeability and clay stabilization, was observed.
For most oils tested, the CO2/CO mixture increased rate of oil recovery by 2-3X, using only 50-60% as much gas/bo as compared to pure CO2. Recovery factors of 80%, at immiscible pressures 30-40% below CO2 MMP, were achieved. Addition of 15% N2 (v/v) to the CO2/CO mixture did not impair oil recovery. Interfacial testing (IFT) of oils, using pure CO, demonstrated a lowering of the IFT. RBA testing of asphaltine-rich heavy oils has shown that a mixture of CO2/CO dissolves into the oil at a far faster rate than either CO2 or CO individually and faster than the sum of both individual gases. A similar test using non-asphaltine type oils did not display this unique characteristic. Slim tube testing suggests that CO facilitates the mobilization of asphaltine-rich heavy oils and lowers viscosity. A linear corefloods of a reservoir containing 5% smectite + illite/smectite + and chlorite demonstrated a 275% increase in matrix permeability. Packed column tests, containing quartz sand and bentonite, demonstrated up to 300-900% increase in permeability in the presence of CO.
Thus a method to recover oil faster, from stranded reservoirs, at pressures below MMP, using significantly less gas, appears possible. In addition the use of CO, either alone or in combination with CO2 and/or N2, has been shown to increase matrix permeability. Such a gas mixture may be beneficial to achieving low pressure EOR from shallow, "stranded" reservoirs, non-conventional shale oil reservoirs, and viscous, heavy oil reservoirs at low temperatures. Incorporation of CO, or CO2/CO, in a frac fluid, or alternately as a post frac cleanup for shale oil and gas applications appears to warrant investigation.
Aldhaheri, Munqith N. (Missan Oil Company, Missouri University of Science and Technology) | Wei, Mingzhen (Missouri University of Science and Technology) | Bai, Baojun (Missouri University of Science and Technology)
Polymer gels are increasingly applied to improve sweep efficiency of different IOR/EOR recovery processes. Three in-situ polymer gel systems including bulk gels, colloidal dispersion gels, and weak gels are often used to mitigate water production caused by reservoir heterogeneity and unfavorable mobility ratio of oil and injected fluids. Selecting the most appropriate gel system is a key component for a successful conformance improvement treatment. Screening criteria in terms of reservoir and fluid characteristics have been widely used to identify potential technologies for a specific reservoir. Despite the large number of polymer gel projects, only five, limited-parameters, single-agent criteria or surveys have been sporadically accomplished that suffer from many deficiencies and drawbacks.
This paper presents the first complete applicability guidelines for gel technologies based on their field implementations in injection wells from 1978 to 2015. The data set includes 111 cases histories compiled mainly from SPE papers and U.S. Department of Energy reports. We extracted missing data from some public EOR databases and detected potential outliers by two approaches to ensure data quality. Finally, for each parameter, we evaluated project and treatment frequency distributions and applicability ranges based on successful projects. Extensive comparisons of the developed applicability criteria with the previous surveillance studies are provided and differences are discussed in details as well.
In addition to the parameters that are considered for other EOR technologies, we identified that the applicability evaluations of polymer gels should incorporate the parameters that depict roots and characteristics of conformance issues. The present applicability criteria comprise 16 quantitative parameters including permeability variation, mobility ratio, and three production-related aspects. Application guidelines were established for organically crosslinked bulk gels for the first time, and many experts' opinions in the previous criteria were replaced by detailed property evaluations. In addition, we identified that the applicability criteria of some parameters are considerably influenced by lithology and formation types, and thus, their data were analyzed according to these characteristics. Besides their comprehensiveness of all necessary screening parameters, the novelty of the new criteria lies in their ability to self-check the established validity limits for the screening parameters which resulted from the inclusion and simultaneous evaluation of the project and treatment frequencies.
Mishra, Ashok (Conoco Phillips) | Abbas, Sayeed (Conoco Phillips) | Braden, John (Conoco Phillips) | Hazen, Mike (Conoco Phillips) | Li, Gaoming (Conoco Phillips) | Peirce, John (Conoco Phillips) | Smith, David D. (Conoco Phillips) | Lantz, Michael (TIORCO, a Nalco Champion Company)
This paper is a field case review of the process and methodologies used to identify, characterize, design, and execute a solution for a waterflood conformance problem in the Kuparuk River Unit in late 2013. In addition, post treatment analysis in a complex WAG flood will be discussed. The Kuparuk River Field is a highly fractured and faulted, multi-layer sandstone reservoir located on the North Slope of Alaska. Large scale water injection in the field was initiated in 1981 and overall the field responded favorably to waterflood operations. In 1996, Kuparuk implemented a miscible WAG flood in many areas of the field. However, natural fault and fracture connectivity has resulted in some significant conformance issues between high angle wells in the periphery. Methodologies employed to identify and characterize one specific conformance issue will be outlined. Details of diagnostic efforts, and how they were used to identify, characterize and mitigate an injector/producer interaction through a void space conduit will be discussed. The solution selected to resolve this conformance issue involved pumping a large crosslinked hydrolyzed polyacrylamide (HPAM) gel system. The solution used a tapered concentration design with one of the highest molecular weight HPAM polymers available. Before execution of this solution, extensive history matching and modeling of the solution design and benefits were used to justify this effort. These modeling efforts and their projections will be reviewed. This solution was pumped into the offending injector in late 2013, and offset producers were carefully monitored for gel breakthrough. The polymer treatment design parameters, including rates and pressure limits were used to generate an effective solution. A discussion of this active design approach, a complete review of the well problem dynamics, treatment operations, products used, and potential complications associated with these products will be discussed. Post solution execution performance analysis was difficult due to the active nature of this MWAG flood. A variety of plotting and analysis techniques were used to identify and quantify the results. A discussion of these results will be provided. Finally, a summary of lessons learned, and a limited discussion of future plans will be presented.
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.