We study the enhanced mass transfer of CO2 in water for a CO2 saturated layer on top of a water saturated porous medium, experimentally and theoretically. A relatively large experimental set-up with a length of 0.5 m and a diameter of 0.15 m is used in pressure decay experiments to minimize the error of pressure measurement due to temperature fluctuations and small leakages. The experimental results were compared to the theoretical result in terms of onset time of natural convection and rate of mass transfer of CO2 in the convection dominated process. In addition, a non-isothermal multicomponent flow model in porous media, is solved numerically to study the effect of the heat of dissolution of CO2 in water on the rate of mass transfer of CO2. The effect of the capillary transition zone on the rate of mass transfer of CO2 is also studied theoretically. The simulation results including the effect of the capillary transition zone show a better agreement with experimental results compared to the simulation result without considering a capillary transition zone. The simulation results also show that the effect of heat of dissolution on the rate of mass transfer is negligible @en

Carbonated water flooding (CWI) increases oil production due to favorable dissolution effects and viscosity reduction. Accurate modeling of CWI performance requires a simulator with the ability to capture the true physics of such process. In this study, compositional modeling coupled with surface complexation modeling (SCM) are done, allowing a unified study of the influence in oil recovery of reduction of salt concentration in water. The compositional model consists of the conservation equations of total carbon, hydrogen, oxygen, chloride and decane. The coefficients of such equations are obtained from the equilibrium partition of chemical species that are soluble both in oleic and the aqueous phases. SCM is done by using the PHREEQC program, which determines concentration of the master species. Estimation of the wettability as a function of the Total Bound Product (TBP) that takes into account the concentration of the complexes in the aqueous, oleic phases and in the rock walls is performed. We solve analytically and numerically these equations in 1 - D in order to elucidate the effects of the injection of low salinity carbonated water into a reservoir containing oil equilibrated with high salinity carbonated water.@en

A method based on the concept of exergy-return on exergy-investment is developed to determine the energy efficiency and CO2 intensity of polymer and surfactant enhanced oil recovery techniques. Exergy is the useful work obtained from a system at a given thermodynamics state. The main exergy investment in oil recovery by water injection is related to the circulation of water required to produce oil. At water cuts (water fraction in the total liquid produced) greater than 90%, more than 70% of the total invested energy is spent on injection and lift pumps, resulting in large CO2 intensity for the produced oil. It is shown that injection of polymer with or without surfactant can considerably reduce CO2 intensity of the mature waterflood projects by decreasing the volume of produced water and the exergy investment associated with its circulation. In the field examples considered in this paper, a barrel of oil produced by injection of polymer has 2–5 times less CO2 intensity compared to the baseline waterflood oil. Due to large manufacturing exergy of the synthetic polymers and surfactants, in some cases, the unit exergy investment for production of oil could be larger than that of the waterflooding. It is asserted that polymer injection into reservoirs with large water cut can be a solution for two major challenges of the energy transition period: (1) meet the global energy demand via an increase in oil recovery and (2) reduce the CO2 intensity of oil production (more and cleaner energy).@en

Production of mature oil fields emits significant amount of CO2 related to circulation and handling of large volumes of gas and water. This can be reduced either by (1) using a low-carbon energy source and/or (2) reducing the volumes of the non-hydrocarbon produced/injected fluids. This paper describes how improved oil recovery techniques can be designed to reduce CO2 intensity (kgCO2/bbl oil) of oil production by efficient use of the injectants. It is shown that CO2 emissions associated with injection of chemicals is strongly influenced by water cut at the start of the project, extent of the water cut reduction, and chemical utilization factor defined as the volume of produced oil per mass or volume of the injectant. As an example, for the oil field considered in this study, 3–8% reduction in water cut can result in 50–80% reduction in its CO2 intensity. In addition to the incremental oil production with lower CO2 intensity, the earlier implementation of enhanced oil recovery methods can extend the lifetime of the mature fields if carbon emission cut-offs are applied. In case of CO2 enhanced oil recovery (EOR), the large storage potential for CO2 can significantly reduce the overall CO2 emissions of oil, albeit at a large energetic cost. For CO2 EOR using CO2 captured from gas power plants, improving the utilization factor from 2 bbl/tCO2 to 4 bbl/tCO2 can reduce the CO2 intensity of the produced oil from 120 kgCO2/bbl to 80 kgCO2/bbl (33% reduction).@en

Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine with a different composition than that of the in situ brine is injected into cores with and without remaining oil saturation. The cation-exchange capacity (CEC) of the rocks was calculated using PHREEQC software (coupled to a multipurpose transport simulator) with the ionic composition of the effluent histories as input parameters. We observe that in the presence of crude oil, ion exchange is a kinetically controlled process and its rate depends on residence time of the oil in the pore, the temperature, and kinetic rate of adsorption of the polar groups on the rock surface. The cation-exchange process occurs in two stages during two phase flow in porous media. Initially, the charged sites of the internal surface of the clays establish a new equilibrium by exchanging cations with the aqueous phase. At later stages, the components of the aqueous and oleic phases compete for the charged sites on the external surface or edges of the clays. When there is sufficient time for crude oil to interact with the rock (i.e., when the core is aged with crude oil), a fraction of the charged sites are neutralized by the charged components stemming from crude oil. Moreover, the positively charged calcite and dolomite surfaces (at the prevailing pH environment of our experiments) are covered with the negatively charged components of the crude oil and therefore less mineral dissolution takes place when oil is present in porous media.@en

Recent developments in Radio Frequency (800 MHz–1000 MHz) Identification (RFID) devices suggest that it is possible to use them for wireless laboratory measurements of the dielectric coefficients (or compositions) of fluid mixtures with possible spin-off for their use in the petroleum engineering practice. The advantage of RFID devices is their small size (0.095×0.008×0.001 m3), the developments to make them increasingly smaller and that they do not require the use of leak prone connecting cables. RFID measures the response of a sample volume of interest irradiated by a radio frequency electromagnetic (EM) wave. The response can be expressed in terms of various response functions, e.g. two scattering functions (S11 and S21) or the minimum irradiated power (Pmin). The response functions can be measured using a state-of-the-art RFID device (CISC RFID Xplorer-200), which operates in the range between 800 and 1000 MHz. The effect of the dielectric coefficient on the RFID response was tested by placing the RFID tag in different media with various dielectric coefficients ε ranging from 1 to 80. The overall purpose is to develop a work-flow to relate the response functions obtained with RFID technology to the dielectric coefficient and thus the composition of fluid mixtures in which an RFID tag can be immersed. An application is to measure fluid compositions during a spontaneous imbibition experiment in an Amott-cell. As an intermediate step we measure the composition dependence of the partial molar volume of diethyl ether (DEE) in brine and the partial molar volume of DEE in oil by using an Anton Paar density meter. The relation between the dielectric coefficients and the volume fraction can be obtained with the Böttcher mixing rule. The DEE volume fraction range of interest is 0–8% volume fraction in the aqueous solution whereas DEE volume fraction range of interest is 0–100% volume fraction in oleic solutions. For better understanding of the measurement results, we used COMSOL™ simulations, which show that the response functions depend on the dielectric coefficient in a vessel of appropriate dimensions filled with a fluid of choice. The measurements show that the minimum power at the tag position Pmin is the preferred response function and that the sensitivity of Pmin was highest at 915 and 868 MHz for aqueous (8.547×10−6) and oleic (1.905×10−4) solutions respectively. The measurement error is of the same order of magnitude as the errors mentioned above (Hon, 1989) ensuing from evaporation of DEE during the preparation of the calibration fluids or the approximate nature of the Böttcher mixing rule. We conclude that it is possible to use RFID technology for contact-less measurements of the compositions of fluids in imbibition experiments.@en

Recently, there is an increased interest in reactive flow in porous media, in groundwater, agricultural and fuel recovery applications. Reactive flow modeling involves vastly different reaction rates, i.e., differing by many orders of magnitude. Solving the ensuing model equations can be computationally intensive. Categorizing reactions according to their speeds makes it possible to greatly simplify the relevant model equations. Indeed some reactions proceed so slow that they can be disregarded. Other reactions occur so fast that they are well described by thermodynamic equilibrium in the time and spatial region of interest. At intermediate rates kinetics needs to be taken into account. In this paper, we categorize selected reactions as slow, fast or intermediate. We model 2D radially symmetric reactive flow with a reaction-convection-diffusion equation. We show that we can subdivide the PeDaII phasespace in three regions. Region I (slow reaction); reaction can be ignored, region II (intermediate reaction); initially kinetics need to be taken into account, region III (fast reaction); all reaction takes places in a very narrow region around the injection point. We investigate these aspects for a few specific examples. We compute the location in phase space of a few selected minerals depending on salinity and temperature. We note that the conditions, e.g., salinity and temperature may be essential for assigning the reaction to the correct region in phase space. The methodology described can be applied to any mineral precipitation/decomposition problem and consequently greatly simplifies reactive flow modeling in porous media.@en

1D water oil displacement in porous media is usually described by the Buckley-Leverett equation or the Rapoport-Leas equation when capillary diffusion is included. The rectilinear geometry is not representative for near well oil displacement problems. It is therefore of interest to describe the radially symmetric Buckley-Leverett or Rapoport-Leas equation in cylindrical geometry (radial Buckley-Leverett problem). We can show that under appropriate conditions, one can apply a similarity transformation (r, t) → η= r2/ (2 t) that reduces the PDE in radial geometry to an ODE, even when capillary diffusion is included (as opposed to the situation in the rectilinear geometry (Yortsos, Y.C. (Phys. Fluids 30(10),2928–2935 1987)). We consider two cases (1) where the capillary diffusion is independent of the saturation and (2) where the capillary diffusion is dependent on the saturation. It turns out that the solution with a constant capillary diffusion coefficient is fundamentally different from the solution with saturation-dependent capillary diffusion. Our analytical approach allows us to observe the following conspicuous difference in the behavior of the dispersed front, where we obtain a smoothly dispersed front in the constant diffusion case and a power-law behavior around the front for a saturation-dependent capillary diffusion. We compare the numerical solution of the initial value problem for the case of saturation-dependent capillary diffusion obtained with a finite element software package to a partially analytical solution of the problem in terms of the similarity variable η.@en

It has been estimated that 17% of the recovered hydrocarbon exergy in oil fields [1]is spent on fluid handling and recovery costs. Therefore, improving the efficiency of oil production can give an some contribution to more efficient energy usage and therefore minimizing to some extent the carbon footprint. By way of example we present in this paper a work-flow, which can serve as a template for computing the fluid handling and recovery costs for natural polymer (Guar-Arabic Gum)flooding. The main contributors to the exergy investment in an Exergy Return on Exergy Investment analysis (ERoEI)are, the fluid circulation costs, the steel costs of the tubing and casing and to some degree the drilling costs. The main contributor to the exergy gain is the exergy of the produced oil. The fluid circulation costs represent the largest exergy investment and usually approximately accounts for 80% of the exergy used for the recovery of oil. For quantifying the circulation costs, the paper uses a 1-D displacement model of polymer flooding of oil to compare the enhanced oil recovery (EOR)history for three scenarios, i.e., (1)water injection, (2)natural-polymer water injection and (3)natural-polymer slug injection. The advantage of a 1-D model is that it allows multiple comparisons of many scenario's avoiding time consuming simulations but this goes at the expense of ignoring 3-D effects. The 1-D model can be extended to a 2-D or 3-D model, which makes it possible to include the improvement of vertical and areal sweep-efficiency. A numerical solution of the EOR model is obtained with COMSOL. We analyze the exergy balance of viscosified water, e.g., with natural-polymer. A comparison as to the displacement efficiency is made between the three scenarios, viz., water, Guar-Arabic gum, and slug injection. The viscosity behavior of Guar-Arabic gum is obtained from laboratory data. It is argued that an ERoEI analysis, which is used on its own or complementary to an economic analysis, can be used to show the advantage of using Guar-Arabic gum slugs with respect to permanent polymer-injection to enhance the oil recovery. Moreover, the analysis shows that at the end of the project, the concept of exergy-zero recovery time or zero-time marks, for each scenario the termination point, i.e., when the circulation exergy costs (exergy investment)become equal to the recovery exergy (exergy return), and thus recovery should be abandoned. For the conditions considered a single polymer injection displacement leads to optimal results.@en

This paper presents an assessment of the life-cycle exergetic efficiency and CO2 footprint of the underground biomethanation process. The subsurface formation, hosting microorganisms required for the reaction, is utilized to convert CO2 and green (produced from renewable energy) hydrogen to the so-called "green"or synthetic methane. The net exergy gain and CO2 intensity of the biomethanation process are compared to the alternative options of (1) green H2 storage (no energy upgrading process to CH4) and (2) fossil-based CH4 with carbon capture and storage (CCS), i.e., blue CH4. It is found that with the current state of the technology and within the assumptions of this study, the exergy return on the exergy invested for underground biomethanation does not outperform the direct storage and utilization of green H2. The maximum exergetic efficiency of the biomethanation process is calculated to be 15-33% for electricity and 36-47% for heating, while the overall exergetic efficiency of the direct use of H2 for electricity is estimated to be between 20 and 61%. Moreover, the energy produced from the underground biomethanation process has the largest CO2 intensity among the studied options. Depending on the technology used in the CCS and hydrogen production stages, the CO2 intensity of the electricity generated from synthetic CH4 can be as large as 142 g CO2/MJe, which is at least 56-73% larger than those of the two other studied cases. @en

This work uses pilot examples of CO2 enhanced oil recovery to analyze whether and under which circumstances it is exergetically favorable to sequester CO2 through enhanced oil recovery. We find that the net storage efficiency (ratio between the stored and captured CO2) of the carbon capture and storage (CCS)-only projects is maximally 6–56% depending on the fuel used in the power plants. With the current state of technology, the CCS process will re-emit a minimum of 0.43–0.94 kg of CO2 per kg of CO2 stored. From thermodynamics point of view, CO2 enhanced oil recovery (EOR) with CCS option is not sustainable, i.e., during the life cycle of the process more energy is consumed than the energy produced from oil. For the CCS to be efficient in reducing CO2 levels (1) the exergetic cost of CO2 separation from flue gas should be reduced, and/or (2) the capture process should not lead to additional carbon emission. Furthermore, we find that the exergy recovery factor of CO2-EOR depends on the CO2 utilization factor, which is currently in the low range of 2–4 bbl/tCO2 based on the field data. Exergetically, CO2 EOR with storage option produces 30–40% less exergy compared to conventional CO2 enhanced oil recovery projects with CO2 supplied from natural sources; however, this leads to storage of >400 kg of extra CO2 per barrel of oil produced.@en

In hydraulic fracturing, fracturing fluids are used to create fractures in a hydrocarbon reservoir throughout transported proppant into the fractures. The application of many fields proves that conventional fracturing fluid has the disadvantages of residue(s), which causes serious clogging of the reservoir's formations and, thus, leads to reduce the permeability in these hydrocarbon reservoirs. The development of clean (and cost-effective) fracturing fluid is a main driver of the hydraulic fracturing process. Presently, viscoelastic surfactant (VES)-fluid is one of the most widely used fracturing fluids in the hydraulic fracturing development of unconventional reservoirs, due to its non-residue(s) characteristics. However, conventional single-chain VES-fluid has a low temperature and shear resistance. In this study, two modified VES-fluid are developed as new thickening fracturing fluids, which consist of more single-chain coupled by hydrotropes (i.e., ionic organic salts) through non-covalent interaction. This new development is achieved by the formulation of mixing long chain cationic surfactant cetyltrimethylammonium bromide (CTAB) with organic acids, which are citric acid (CA) and maleic acid (MA) at a molar ratio of (3:1) and (2:1), respectively. As an innovative approach CTAB and CA are combined to obtain a solution (i.e., CTAB-based VES-fluid) with optimal properties for fracturing and this behaviour of the CTAB-based VES-fluid is experimentally corroborated. A rheometer was used to evaluate the visco-elasticity and shear rate & temperature resistance, while sand-carrying suspension capability was investigated by measuring the settling velocity of the transported proppant in the fluid. Moreover, the gel breaking capability was investigated by determining the viscosity of broken VES-fluid after mixing with ethanol, and the degree of core damage (i.e., permeability performance) caused by VES-fluid was evaluated while using core-flooding test. The experimental results show that, at pH-value (6.17), 30 (mM) VES-fluid (i.e., CTAB-CA) possesses the highest visco-elasticity as the apparent viscosity at zero shear-rate reached nearly to 106 (mPa·s). Moreover, the apparent viscosity of the 30 (mM) CTAB-CA VES-fluid remains 60 (mPa·s) at (90 °C) and 170 (s-1) after shearing for 2-h, indicating that CTAB-CA fluid has excellent temperature and shear resistance. Furthermore, excellent sand suspension and gel breaking ability of 30 (mM) CTAB-CA VES-fluid at 90 (°C) was shown; as the sand suspension velocity is 1.67 (mm/s) and complete gel breaking was achieved within 2 h after mixing with the ethanol at the ratio of 10:1. The core flooding experiments indicate that the core damage rate caused by the CTAB-CA VES-fluid is (7.99%), which indicate that it does not cause much damage. Based on the experimental results, it is expected that CTAB-CA VES-fluid under high-temperature will make the proposed new VES-fluid an attractive thickening fracturing fluid.@en

This paper deals with on line viscosity measurements using integrated circuit technology, and is building on a previous paper on the use radio frequency identifier (RFID) technology for determining dielectric coefficients. It is asserted that the progress in RFID technology and integrated circuits, in particular in micro–electro–mechanical system (MEMS) makes it possible to combine them to perform physico-chemical property measurements using devices on centimeter scale. It can even be expected that these devices can be made increasingly smaller. An important property of interest is the viscosity, in this specific case, for the use of Arabic gum in enhanced oil recovery. Arabic gum, is an environmentally acceptable natural product. Natural-polymer solutions 1000 [ppm] are more viscous and therefore more efficient oil displacement agents. They require less invested exergy than non-viscosified water to recover oil. However, polymers, in particular environmentally acceptable natural-polymers (e.g., Guar–Arabic gum) available in large quantities in India and Sudan, are susceptible to microbial degradation. It is therefore important to monitor its quality at the injection and production side for real-time quality control. Natural-polymers based on plant products are promising EOR agents. They may have a lower environmental footprint because of the biodegradability. To provide a proof of concept, we use a state of the art acoustic wave sensor (AWS), which can determine acoustic viscosities. It is asserted that RFID technology can be used to record the acoustic wave signal (SenGenuity vismart acoustic wave Sensor AWS) to determine the viscosity at some distance (meters) away from the measurement device. A calibration with solutions of known viscosity behavior (i.e., Glycerol) can be used to relate the acoustic viscosity to the dynamic viscosity. We can calibrate the acoustic wave sensor using Guar–Arabic gum solutions to measurements with the Anton Paar viscometer (MCR-302). For the glycerol solution we also compare to reported literature data. The Newtonian viscosity measurements of the Paar density meter, and the literature values agree within a few percent. These favorable comparisons, are an important step in developing a methodology that allows cutting edge RFID-IC technology for real-time non-contact monitoring of viscosity degradation.@en

This contribution focuses on surface complexes in the calcite-brine-surfactant system. This is relevant for the recovery of oil when using a new hybrid enhanced oil recovery (EOR) method, which combines smart-water (i.e., ionically modified brine) and foam-flooding (SWAF) of light oil with dissolved carbon dioxide (CO2) at high pressure in carbonate (i.e., calcite) reservoirs. Using this new hybrid EOR-method (i.e., the SWAF-process) is not only economically attractive (i.e., it reduces opex costs) but also enhances the effectiveness of the production process, and thus reduces the environmental impact. Ionically modified brine (i.e., low-salinity) has a dual improvement effect. It not only leads to more stable foam lamellae, but also helps to change the carbonate rock wettability, leading for some conditions to more favorable relative permeability behavior. The mechanism for the modified permeability behavior in the presence of ionically modified brine is only partly understood. Therefore, we study this process initially in a zero dimensional (thermodynamics) setting, which can be used for the one dimensional (1D) displacement process with an oleic phase that contains carbon dioxide (CO2) and an aqueous phase that contains both carbon dioxide (CO2) and all the ionic substances. Using DLVO theory and surface complexation modeling to better understand the mechanism(s) of ionically modified brine as wettability modifier and foam stabilizer. We perform simulations using both (NaCl) and (MgCl2) to show the effect of a divalent ion at the high-salinity (8500 mmol/kg-w) and low-salinity (0.4 mmol/kg-w) for both ambient-conditions at (25°C) and at the reservoir-conditions (80°C). We confine our analysis to a description that uses the Dzombak-Morel model of surface complexes, which is based on the Debye-Hückel theory (i.e., valid up to ionic strength of 0.3 (mol/kilogram of water)). We also investigate the effect of carbon dioxide (CO2) on the stability of low-salinity foam-laminae. We model the foam-laminae, which contain as surface complex a (cationic) surfactant in an aqueous phase. We use the PHREEQC-software to calculate the surface charge and the surface potential. The presence of a carbon dioxide (CO2) phase leads to dissolution of four valent C(IV) compounds in the aqueous film. PHREEQC also calculates the equilibrium concentrations and surface potential and allows the study of the effect of salinity and the carbon dioxide (CO2) gas pressure. For the soap-film (foam-film) in a carbon dioxide (CO2) atmosphere we do use Pitzer activity coefficients (i.e., valid up to 6 (mol/kilogram of water)). As our aim is to show the methodology and the versatility of this approach, we leave more realistic choices of these parameters for future work.sFor the conditions considered we can qualitatively state that, in the presence of (NaCl i.e., at pH > 10) and (MgCl2 i.e., pH > 10.3), the low-salinity case shows a more stable water-film behavior at (25°C) and at (80°C) than the high-salinity case for both (25°C) and (80°C). Moreover, high carbon dioxide (CO2) pressures have a destabilizing effect on the film, as they reduce the surface potential. A reduced surface potential leads to a decreasing electrostatic double layer repulsion and thus destabilizes the foam-film, whereas low-salinity leads to less screening of the surface potential and thus improves the stability of the foam-film. The low-salinity flow is characterized by a high residual oil saturation and low end-point permeability for the two phase oil-water flow. This leads to a more favorable mobility ratio and thus a more favorable displacement process. For the calcite surface an enhanced stability helps to stabilize the water film on the calcite surface if the oil-water surface charge has the same sign as the surface charge on the calcite surface. Our calculations show the pH range where the sign of these charges is the same or opposite at low-salinity and high-salinity conditions. Admittedly these calculations only show trends, but can be used to delineate optimal conditions for the application of “Smart Water Assisted Foam (SWAF) Flooding”. It is expected that the SWAF-process under the optimum conditions will make the proposed new hybrid Enhanced Oil Recovery (EOR) process environmentally and economically attractive.@en