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.
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.
Polymer flooding is a proven technology to improve sweep efficiency, while being one of the most economical enhanced oil recovery (EOR) processes. Partially hydrolyzed polyacrylamide (HPAM) has been widely used for polymer flooding. As the HPAM usage for EOR increases, the challenge of produced water management is also raised because residual HPAM in produced water could increase total chemical oxygen demand and unwanted viscosity in discharging or re-injecting the water. As the environmental standards and regulations get more stringent, it is difficult for the conventional methods to meet the requirement for discharging. Use of magnetic nanoparticles (MNPs) to remove contaminants from produced water is a promising way to treat produced water in an environmentally green way with minimal use of chemicals. The main attraction for MNPs is their quick response to move in a desired direction with application of external magnetic field. Another attraction of MNPs is versatile and efficient surface modification through suitable polymer coating, depending on the characteristics of target contaminants. In this study, we investigate the feasibility of polymer removal using surface-modified MNPs and regeneration of spent MNPs for multiple re-use.
The electrostatic attraction between negatively charged HPAM polymer and positively charged MNPs controls the attachment of MNPs to HPAM molecular chain; and the subsequent aggregation of the now neutralized MNP-attached HPAM plays a critical role for accelerated and efficient magnetic separation.
Although geochemical reactions are the fundamental basis of the alkaline/surfactant/polymer (ASP) flooding, their importance is commonly overlooked and not fully assessed. Common assumptions made when modeling geochemical reactions in ASP floods include: 1) ideal solution (i.e., using molalities rather than ion activities) for the water and aqueous geochemical species 2) limiting the number of reactions (i.e., oil/alkali and alkali consumptions) rather than including the entire thermodynamically-equilibrated system 3) ignoring the effect of temperature and pressure on reactions 4) local equilibrium ignoring the kinetics. To the best of our knowledge, the significance of these assumptions has never been discussed in the literature. In this paper we investigate the importance of geochemical reactions during alkaline/surfactant/polymer floods using a comprehensive tool in the sense of surfactant/soap phase behavior as well as geochemistry.
We coupled the United States Geological Survey (USGS) state-of-the-art geochemical tool, with 3D flow and transport chemical flooding module of UTCHEM. This geochemical module includes several thermodynamic databases with various geochemical reactions, such as ion speciation by applying several ion-association aqueous models, mineral, solid-solution, surface-complexation, and ion-exchange reaction. It has capabilities of saturation index calculation, reversible and irreversible reactions, kinetic reaction, mixing solutions, inverse modeling and includes impacts of temperature and pressure on reaction constants and solubility products. The chemical flood simulator has a three phase (water, oil, microemulsion) phase behavior package for the mixture of surfactant/soap, oil, and water as a function of surfactant/soap, salinity, temperature, and co-solvent concentration. Hence, the coupled software package provides a comprehensive tool to assess the significance of geochemical assumptions typically imposed in modeling ASP floods. Moreover, this integrated tool enables modeling of variations in mineralogy present in reservoir rocks. We parallelized the geochemistry module of this coupled simulator for large-scale reservoir simulations.
Our simulation results show that the assumption of ideal solution overestimates ASP oil recovery. Assuming only a subset of reactions for a coupled system is not recommended, particularly when a large number of geochemical species is involved, as is the case in realistic applications of ASP. Reservoir pressure has a negligible effect but temperature has a significant impact on geochemical calculations. Although mineral reaction kinetics is largely a function of the temperature and in-situ water composition, some general conclusions can be drawn as follows: to a good approximation, minerals with slow rate kinetic reaction (e.g., quartz) can be excluded when modeling ASP laboratory floods. However, minerals with fast rate kinetic reactions (e.g., calcite) must be included when modeling lab results. On the other hand, in modeling field-scale applications, local equilibrium assumption (LEA) can be applied for fast rate kinetic minerals, whereas kinetics should be used for slow rate kinetic minerals.
Polymer flooding can significantly improve sweep and delay breakthrough of injected water, thereby increasing oil recovery. Polymer viscosity degrades in reservoirs with high salinity brines, so it is advantageous to inject low salinity water as a preflush. Low salinity water flooding (LSW) can also improve local displacement efficiency by changing the wettability of the reservoir rock from oil wet to more water wet. The mechanism for wettability alteration for low salinity waterflooding in sandstones is not very well understood, however experiments and field studies strongly support that cation exchange (CE) reactions are the key element in wettability alteration. The complex coupled effects of CE reactions, polymer properties, and multiphase flow and transport has not been explained to date.
This paper presents the first analytical solutions for the coupled synergistic behavior of low salinity waterflooding and polymer flooding considering cation exchange reactions, wettability alteration, adsorption, inaccessible pore volume (IPV), and salinity effects on polymer viscosity. A mechanistic approach that includes the cation exchange of Ca2+, Mg2+ and Na+ is used to model the wettability alteration. The aqueous phase viscosity is a function of polymer and salt concentrations. Then, the coupled multiphase flow and reactive transport model is decoupled into three simpler sub-problems, one where cation exchange reactions are solved, the second where a variable polymer concentration can be added to the reaction path and the third where fractional flows can be mapped onto the fixed cation and polymer concentration paths. The solutions are used to develop a front tracking algorithm, which can solve the slug injection problem where low salinity water is injected as a preflush followed by polymer. The results are verified with experimental data and PennSim, a general purpose compositional simulator.
The analytical solutions show that decoupling allows for estimation of key modeling parameters from experimental data, without considering the chemical reactions. Recovery can be significantly enhanced by a low salinity pre-flush prior to polymer injection. For the cases studied, the improved oil recovery (IOR) for a chemically tuned LSP flood can be as much as 10% OOIP greater than with considering polymer alone. The results show the structure of the solutions, and in particular the velocity of multiple shocks that develop. These shocks can interact, changing recovery. For example, poor recoveries obtained in core floods for small low salinity slug sizes are explained with intersection of shocks without considering mixing. The solutions can also be used to benchmark numerical solutions and for experimental design. We demonstrate the potential of LSP as a cheaper and more effective way for performing polymer flooding when the reservoir wettability can be altered using chemically-tuned low salinity brine.