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.
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.
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.
Suarez, Ricardo G. Suarez (SPE University of Calgary) | Scott, Carlos E. (SPE University of Calgary) | Pereira-Almao, Pedro (SPE University of Calgary) | Hejazi, S. Hossein (SPE University of Calgary)
Nanocatalytic in-situ upgrading is a novel oil recovery method that involves chemical, thermal and miscible processes. In this work the main oil recovery mechanisms of nanocatalytic in-situ upgrading were studied, particularly the ones that promote additional oil production from low matrix permeability blocks.
Heavy oil recovery from Silurian dolomite cores was studied using a cylindrical core holder set-up. Fractures in the system were represented by a gap between the core sample and core holder wall. Oil recovery experiments were conducted in batch-mode using hydrogen and a trimetallic nano-catalyst. The cores were fully saturated with heavy-oil and the fractures were filled with hydrogen and vacuum residue with ultra-dispersed nano-catalyst at 300 °C and 1000 psig. The produced oil from the matrix was collected and the recovery factor for each experiment was calculated. Moreover, the residual oil in the core was extracted using a solvent. Both samples (i.e., produced and residual oil) were characterised by laboratory measurements and analytical techniques in order to assess oil quality distribution.
Experimental results revealed a significant increment in oil recovery with hydrogen injection. This increment suggests that during nanocatalytic in-situ upgrading oil is produced due to the presence of hydrogen in gas form. Results also demonstrated that, by use of an ultra-dispersed Ni-W-Mo nano-catalyst, the oils contained in both the fracture and matrix, were upgraded.
This research fosters the understanding of the main recovery mechanisms from carbonate matrix blocks by use of nanocatalytic in-situ upgrading. This study contributes to better understanding a recovery technique that will unlock heavy-oil resources contained in carbonate rocks.
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.
Tagavifar, Mohsen (The University of Texas at Austin) | Herath, Sumudu (The University of Texas at Austin) | Weerasooriya, Upali P. (The University of Texas at Austin) | Sepehrnoori, Kamy (The University of Texas at Austin) | Pope, Gary (The University of Texas at Austin)
We made measurements of microemulsion rheology with mixtures of oil, brine, surfactant, co-solvent, and in some cases polymer to systematically investigate the effects of salinity, co-solvents and polymers. A microemulsion rheology model was developed and used to interpret the experimental results. We show that the optimum microemulsion-to-oil viscosity ratio is roughly 5 to 6 without co-solvent, but it can be reduced to a more favorable ratio of ~2 by adding co-solvent. Even though the amount of co-solvent needed is case dependent, a clear trend of microemulsion viscosity reduction with increasing co-solvent concentration was observed. Limited evidence suggests that large hydrolyzed polyacrylamide molecules with a narrow molecular weight distribution have negligible partitioning to type II and III microemulsions.
Enhanced-oil-recovery techniques by gas injection in shale reservoirs have been introduced and investigated. Laboratory and simulation works have shown good results for enhanced shale oil recovery, but one problem with gas injection is asphaltene precipitation and deposition. Damage due to asphaltene precipitation and deposition in conventional reservoirs has been reported in the literature. In shale reservoirs, pore and throat sizes are much smaller than in conventional reservoirs. Thus, large asphaltene aggregates may cause more serious problems in shale reservoirs.
This experimental study used a nanofiltration technique to investigate the size of asphaltene aggregates precipitated during CO2 and CH4 injection in a shale oil sample. Nano membranes of 200nm, 100nm and 30nm were used to filtrate oil samples injected with different mole fractions of CO2 and CH4 gas. The distribution of asphaltene aggregates’ size at different injected CO2 and CH4 concentrations were obtained and compared with the pore size distribution data of shale cores measured by mercury intrusion porosimeters. Results showed that a higher injected CO2 and CH4 concentration caused more asphaltene precipitation and growth in asphaltene aggregates’ size. The precipitated asphaltene particle size was large enough to cause a pore-blocking problem in tested shale cores.
Given limited CO2 supply, operational constraints, and pattern specific reservoir performance, WAG schedule can be customized such that NPV or other metrics are optimized. Depending on the WAG schedule, recovery can fluctuate between 5–15% at the pattern scale due to reservoir heterogeneity causing variations in sweep efficiency. An analytical method was developed to optimize WAG schedules that couples traditional reservoir modeling and simulation with machine learning, enabling the discovery of optimal WAG schedules that increase recovery at the pattern level. A history-matched reservoir model of Chaparral Energy's Farnsworth Field, Ochiltree County, TX was sampled intelligently to perform predictive reservoir flow simulations and artificially build an intelligent reservoir model that samples a broad range of possible WAG scenarios for optimization. The intelligent model generates the next "best" sample to investigate in the numerical simulator and converges on the optima, quickly reducing the number of runs investigated. Results in this paper demonstrate that there can be significant improvements in net present value as well as net utilization rates of CO2 using this analytical technique. The WAG design generated by the intelligent reservoir model should be deployed in the field in early 2016 for validation. It is intended that the intelligent reservoir model will be updated on a regular basis as injection and production data is obtained. This effort represents the beginning of a paradigm shift in the application of modeling and simulation tools for significant improvements in field production operations.
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.