This paper examines whether retention of partially hydrolyzed polyacrylamide (HPAM) is different under anaerobic versus aerobic conditions. Both static (mixing with loose sand) and dynamic methods (core floods) were used to determine HPAM retention. There are both advantages and disadvantages associated with determining polymer retention using static tests versus dynamic tests and using aerobic versus anaerobic conditions. From static retention measurements, polymer adsorption values on pure silica sand or Berea sandstone were small, and they showed little difference between experiments conducted aerobically or anaerobically. For both aerobic and anaerobic conditions, HPAM retention increased significantly with increased pyrite or siderite content. Static retention under anaerobic conditions ranged from 45-75 µg/g with 1% of either pyrite or siderite to 137-174 µg/g for 10% pyrite or siderite to 1161-1249 µg/g for 100% pyrite or siderite.
If iron minerals are present, the most representative polymer retention results are obtained (for both static and dynamic tests) if conditions are anaerobic. Retention values (from static measurements) under aerobic conditions were commonly twice those determined under anaerobic conditions. If iron minerals are present and retention tests are performed under aerobic conditions, TOC or some similar method should be used for polymer detection. Viscosity detection of polymer may provide retention values that are too high (because oxidative degradation can be misinterpreted as polymer retention). For a broad range of siderite content, retention from static tests did not depend on whether dissolved oxygen was present. However, for a broad range of pyrite content, HPAM retention was significantly lower in the absence of dissolved oxygen than under aerobic conditions. Theses results may be tied to iron solubility. When polymer solutions were mixed with 100% pyrite over the course of 12 hours, 360–480-ppm iron dissolved into polymer solutions under both aerobic and anaerobic conditions, whereas with 100% siderite, only 0–0.6-ppm iron dissolved. If dynamic methods (i.e., corefloods) are used to determine polymer retention under aerobic conditions, flow rates should be representative of the field application. Rates that are too high lead to underestimation of polymer retention. With 10% pyrite, dynamic retention was 211 µg/g at 6 ft/d versus 43.2 µg/g at 30 ft/d. In contrast, retention values were fairly consistent (40.6 – 47.8 µg/g) between 6 ft/d and 33 ft/d under anaerobic conditions.
Zhang, Yandong (Missouri University of Science and Technology) | Wei, Mingzhen (Missouri University of Science and Technology) | Bai, Baojun (Missouri University of Science and Technology) | Yang, Hongbin (China University of Petroleum) | Kang, Wanli (China University of Petroleum)
Enhanced oil recovery (EOR) processes are regarded as important methods to recover remaining oil after primary and secondary recovery. It is important to select the most appropriate EOR process among the possible techniques for a candidate reservoir. Therefore, EOR screening criteria have been constructed using available EOR data sets and serve as the first step to compare the suitability of each EOR method for a particular reservoir. Most screening criteria for polymer flooding are based on data sets from EOR surveys published biannually by the Oil & Gas Journal. These surveys missed significant polymer flooding parameters such as formation water salinity and hardness, polymer types and molecular weight, polymer concentration, reservoir heterogeneity, and so on. All of these topics are covered in this paper with data from relevant literature and records provided by oil companies in China.
Polymer flooding has been widely applied in China for over 20 years and a large number of pilot and field projects have been conducted. These projects include important information to quantify the development of polymer flooding as an EOR method. Nevertheless, most of them have been published in Chinese, and are not accessible to the global research community due to the language barrier. This paper represents an effort to collect all relevant information of polymer flooding from available Chinese publications and reports from all of the major oil companies in China. The primary objectives of this survey is to reveal EOR advances, to trace the development of the polymer flooding EOR methodology in China, and to benefit EOR worldwide.
This project collected information on 55 polymer flooding projects after reviewing nearly 200 publications in Chinese, including 31 pilot projects and 24 field projects from 1991 to 2014. A data set was constructed by collecting all relevant information for polymer flooding. Statistical analyses and graphical methods were used to analyze the whole data set. Box plots combined with violin plots were used to show the distribution and the range of each parameter. By defining and calculating lower and upper limits in box plots, special projects were identified and explained. Scatter plots, which show multiple parameters in one plot, were used to identify significant relationships among different parameters, especially for dependent parameters. This method overcomes some disadvantages of the range method, which is traditionally used for EOR screening. For example, using polymers with high concentration in low salinity reservoirs can lead to higher incremental oil recovery than in high salinity ones, and lower permeability usually correlates with the use of polymers with lower molecular weight. However, the traditional range method cannot show this relationship. Finally, comprehensive screening criteria for polymer flooding were updated based on information revealed in the field application projects.
This paper addresses two questions for polymer flooding. First, what polymer solution viscosity should be injected? A base-case reservoir-engineering method is present for making that decision, which focuses on waterflood mobility ratios and the permeability contrast in the reservoir. However, some current field applications use injected polymer viscosities that deviate substantially from this methodology. At one end of the range, Canadian projects inject only 30-cp polymer solutions to displace 1000-3000-cp oil. Logic given to support this choice include (1) the mobility ratio in an unfavorable displacement is not as bad as indicated by the endpoint mobility ratio, (2) economics limit use of higher polymer concentrations, (3) some improvement in mobility ratio is better than a straight waterflood, (4) a belief that the polymer will provide a substantial residual resistance factor (permeability reduction), and (5) injectivity limits the allowable viscosity of the injected fluid. At the other end of the range, a project in Daqing, China, injected 150-300-cp polymer solutions to displace 10-cp oil. The primary reason given for this choice was a belief that high molecular weight viscoelastic HPAM polymers can reduce the residual oil saturation below that expected for a waterflood or for less viscous polymer floods. This paper will examine the validity of each of these beliefs.
The second question is: when should polymer injection be stopped or reduced? For existing polymer floods, this question is particularly relevant in the current low oil-price environment. Should these projects be switched to water injection immediately? Should the polymer concentration be reduced or graded? Should the polymer concentration stay the same but reduce the injection rate? These questions are discussed.
Polymer flooding is a widely used commercial process with a low cost per barrel of produced oil, For this application, hydrolyzed polyacrylamide (HPAM) polymers are the most widely used type of polymer. In an era of low cost oil, it is becoming even more essential to optimize the polymer flooding design under realistic reservoir conditions. The objective of this research was to better understand and predict the behavior of HPAM polymers and their effect on residual oil saturation, in order to improve the capability of optimizing field design and performance. The corefloods were performed under typical field conditions of low pressure gradients and low capillary numbers. The polymer floods of the viscous oils recovered much more oil than the water floods, with up to 24% lower oil saturation after the polymer flood than the water flood. The experimental data are in good agreement with the fractional flow analysis using the assumptions that the true residual oil saturations and end point relative permeabilities are the same for both water and polymer. This suggests that for more viscous oils, the oil saturation at the end of water flood (i.e. at greater than 99% water cut) is better described as ‘emaining’ oil saturation rather than the true ‘esidual’ oil saturation. This was true for all of the corefloods regardless of the core permeability and without the need for assuming a permeability reduction factor in the fractional flow analysis.
Pilots are widely used for the purpose of gathering valuable information about performance and practical challenges of implementing a particular CEOR process in a given field (
Addition of chemical species to the material balance equations alongside finer resolution requirements for CEOR simulations compared to waterfloods (WF), often make it impractical to run full field CEOR simulations to the required accuracy. Massively parallel computing, dynamic local grid refinement and sector modeling have been used with varying success, of which sector modeling is the most common. Sector models, by their very definition, are also naturally suited for modeling of pilots.
The art of sector modeling needs mastering a few important steps such as: appropriate selection of the sector model extent, details on carving it out of the Full Field Model (FFM), populating it with proper petrophysical and fluid properties, initializing it to correct initial conditions and optimizing its boundary conditions. On top of that, choice of optimum grid size for proper trade-off of simulation run times and accuracy needs to be considered.
This paper presents a case study for appropriate simulation of a CEOR pilot within Chevron. The candidate has a waterflood history matched FFM. This model is used to generate a sector model for the CEOR pilot area. This paper outlines how the extent of the sector model and all the regions in communication with the Area of Interest (AOI) is decided. It also discusses proper initialization and optimization of the boundary conditions of the sector model along with its appropriate refinement and grid optimization. Proper CEOR simulations on the final optimized sector model and sensitivity analysis are also presented. The challenges, lessons learned and best practices are shared and important considerations for adequate simulation of CEOR processes are outlined.
Water-based polymers are often used to improve oil recovery by increasing displacement sweep efficiency. However, recent laboratory and field work has suggested these polymers, which are often viscoelastic, may also reduce residual oil saturation. The objective of this work is to investigate the effect of viscoelastic polymers on residual oil saturation in Bentheimer sandstones and identify conditions and mechanisms for the improved recovery. Bentheimer sandstones were saturated with a heavy oil (120cp) and then waterflooded to residual oil saturation using brine followed by an inelastic Newtonian fluid (diluted glycerin). These floods were followed by injection of a viscoelastic polymer, hydrolyzed polyacrylamide (HPAM).
Significant reduction in residual oil was observed for all core floods performed at constant pressure drop when the polymer had significant elasticity (determined by the dimensionless Deborah number,
It is now common knowledge among EOR practitioners that the combination of ferrous iron (Fe2+) and oxygen causes severe oxidative degradation to EOR polymers, resulting in a lowering of molecular weight and hence a loss of viscosity. During the design of polymer flooding projects, an important question is thus the acceptable levels of Fe2+ and dissolved oxygen that can be tolerated in injection water specifications. Furthermore, we would like to be able to predict the extent of degradation in the case of excess Fe2+ or oxygen ingress.
However, despite over fifty years of research and a general understanding of the degradation mechanism involved, quantitative prediction of the extent of degradation has proven elusive and dependent on the measurement protocol. This is likely due to the fastidious experimental protocols required to work under anaerobic or limited-oxygen conditions.
We examine existing protocols and demonstrate that experiments in which either Fe2+ or oxygen are the limiting reagent yield equivalent results when the stoechiometry of the Fe2+ oxidation reaction with oxygen is taken into account. Based upon these findings, a novel, easy approach is proposed to quantify polymer oxidative degradation as a function of either dissolved oxygen or Fe2+ content.
The limits of 225 ppb Fe2+ and 32 ppb dissolved oxygen are fixed for Flopaam 3630S in 6 g/l brine in the concentration range 500-1500ppm in order to ensure degradation of low-shear plateau viscosity does not exceed 10%. Higher levels will lead to severe polymer degradation. The influence of polymer concentration, temperature and salinity is also investigated. At last, evolution of redox potential and pH during Fe2+ oxidation are discussed.
There is a direct practical application of these finding for the design of surface facilities for polymer dissolution and transport and for the prediction of degradation in case of oxygen ingress. Moreover, a simple and easily performed protocol is proposed for the evaluation of polymer oxidative degradation.
Lee, Jason (University of Pittsburgh) | Dhuwe, Aman (University of Pittsburgh) | Cummings, Stephen D. (University of Pittsburgh) | Beckman, Eric J. (University of Pittsburgh) | Enick, Robert M. (University of Pittsburgh) | Doherty, Mark (GE Global Research) | O'Brien, Michael (GE Global Research) | Perry, Robert (GE Global Research) | Soong, Yee (US DOE NETL) | Fazio, Jim (US DOE NETL) | McClendon, Thomas R. (US DOE NETL)
CO2 miscible and immiscible displacements and hydrocarbon miscible floods are commonly plagued by low volumetric sweep efficiency, early gas breakthrough, high gas utilization ratios, and significant gas re-compression and recycle. Rather than addressing these problems via the water-alternating-gas (WAG) injection sequence that reduces gas relative permeability or the generation of gas-in-brine foams for reduced mobility, we propose increasing the viscosity of high pressure CO2 or NGL via the dissolution of dilute concentrations of thickening agents.
There are two strategies for increasing the viscosity of high pressure fluids; the dissolution of ultrahigh molecular weight polymers or associating polymers, or the dissolution of small molecules that self-assemble in solution to form viscosity-enhancing linear or helical supramolecular structures. Ideally a very small amount of the thickener will be required (roughly 0.1wt%) to elevate the CO2 or NGL viscosity to the same value as the oil being displaced (typically a 10-100 fold increase). Further, the thickened CO2 or thickened NGL should be a stable, transparent solution that does not require a heating/cooling cycle for viscosity enhancement to occur.
Thickener solubility and viscosity were determined over a 25-100oC range. Each of the three major NGL constituents (ethane, propane and butane) was thickened with an ultrahigh molecular polymer (commercial drag reducing agent), resulting in a 2-30 fold increase in viscosity at polymer concentrations of 0.5wt% or less. The polymer dissolved at the lowest pressure in butane and was most effective as a thickener in butane.
Three small molecule thickeners were identified for the NGL constituents; tri-alkyl-tin fluoride, hydroxyaluminum disoap, and a phosphate ester-crosslinker mixture. Remarkable viscosity enhancements were attained for propane and butane with the tri-alkyl-tin fluoride and aluminum soap; the crosslinked phosphate ester solutions exhibited modest viscosity increases. Only tri-alkyl-tin fluoride thickened ethane.
CO2 thickeners were assessed with a falling ball viscometer and pressure drop associated with flow through Berea sandstone. 4-5 fold increases in viscosity were attained with 1wt% of a high molecular weight polyfluoroacrylate. 3-4 fold increases in viscosity were attained with 1wt% high molecular weight polydimethyl siloxane, but a very large amount of toluene co-solvent was required. Although a remarkably effective small molecule thickener was designed for CO2 (100-fold increase at 1.3wt%), it required a heating/cooling cycle and a very large amount of hexane co-solvent.
We have identified the first polymeric and small molecule thickeners ever reported for ethane. Further, this study presents the largest viscosity increases ever reported for propane and butane with polymers and small molecule thickeners. We have presented the most effective polymeric thickeners for CO2 reported to date. This paper also summarizes numerous molecular architectures that are not viable for CO2 and highlights the most promising compounds that continue to be refined.
One of the primary problems for mature oilfield operators is the production of undesired fluids, such as water or gas. Cantarell is a mature field wherein one of the greatest challenges is managing produced water. Mature oil fields experience severe water production, which can be challenging in naturally fractured carbonate reservoirs that produce through a thick layer of oil. A new technology combining two conformance systems was used to alleviate water production in a well in this field, returning production to optimal levels.
The study well (Well A) was shut in because of high water cut (90 to 100%), and post-analysis of this problem showed water coning from fractures in the Lower Cretaceous formation. The well has a unique interval, and perforating a deeper interval was not possible because the water-oil contact (WOC) was close. The solution selected for this case was a combination of two conformance technologies for water control that permit sealing high permeability channels and fractures and, more importantly, help provide selective water control—one is a swelling polymer designed to shut off water channels, fractures, or highly vugular zones, and the other is hydrocarbon-based slurry cement that reacts on contact with water. The result was the recovery of a producer well with 1,197 BOPD with 14% water cut. After 19 months, production averaged 1,300 BOPD for that month with 40 to 66% water cut.
Correctly diagnosing the problem and combining conformance technologies can help operators resume production of wells considered lost because of undesired fluids production. Therefore, this technology could be used to benefit reservoir optimization and production.
Research has discovered systems that can selectively flocculate mineral solids from a high molecular weight polymer flood matrix while leaving the polymer intact or alternatively achieving a viable total flocculation of the polymer in the produced fluids. Modified alkaline surfactant polymer (ASP) and standard polymer (P) flood systems were studied with findings obtained by controlled variations of both well-proven and non-prevalent chemical approaches. Results concluded that selectively removing the mineral solids from polymer-laden water produces reusable enhanced oil recovery (EOR) fluid.
EOR is a proven method to increase hydrocarbon yield from post-natural, stimulated, or standard flood driven reservoirs. Fluid produced from the reservoir contains the desired hydrocarbon and an aqueous phase. Previously considered a liability, properly treated, the aqueous phase can become an asset. Polymer floods have a proven history in EOR and, though complex in application, ASP also demonstrated EOR effectiveness in the laboratory. Most ASP approaches are currently in field trial stages. The produced fluid is subjected to hydrocarbon separation with the resulting aqueous system either treated for disposal or recycled into the system. The aqueous phase matrix is mainly composed of high molecular weight polymer, mineral solids, residual base, residual oil, and possibly surfactant. If the producer chooses disposal, the solids must be flocculated by a method balancing density, dewaterability, processability, process variability, and cost. However, if the producer opts to recycle the fluid for reinjection, steps must be taken to minimize polymer deviations requiring selective flocculation of all components with exception of the polymer. This undertaking is challenging as EOR polymers are also effective flocculants, therefore sensitive to standard coagulant and flocculant approaches. Utilizing controlled, standard methods and multivariable design of experiments, results were obtained for both total and selective flocculation.
Total flocculation systematically studies the influence of pH, inorganic, and organic coagulants in maximizing the treatment effectiveness. The same approach was successful for selective flocculation, however unique coagulants were applied. The selective flocculation process coagulated and separated the mineral solids, and left the high molecular weight polymer intact and the fluid matrix as viscous as prior to treatment. Effectiveness of treatments were determined using standard gravimetric and viscometric methods.
These discoveries will assist decision makers in determining whether total or selective flocculation is the most viable treatment for polymer based EOR, balancing environmental and economic aspects to pursue a desired treatment route. These methods, though targeting EOR, have practical applications for treatment of flowback and water produced from stimulation and potentially drilling operations as well.