This study is based on the premise that most of the trapped hydrocarbons can be produced, if we substitute them with another ‘acrificial’ fluid that has amplified interactions with organic pore walls, such as CO2. For the presented study, a downhole shale sample is analyzed in the laboratory to predict gas storage properties such as pore-volume, pore compressibility, and gas adsorption capacity. Then a series of pressure pulse decay measurements are performed to delineate transport mechanisms and predict stress-sensitive permeability. These coefficients are obtained as the calibration parameters of a simulation-based optimization for injection and production. Simulation model considers compositional gas flow in a deformable porous media and includes a multi-continuum porosity, with organic and inorganic pores, and micro-fractures. The experimental and simulation results show that most of the injected CO2 is adsorbed in the organic matrix and are not produced back. This is because CO2 molecules have significantly larger adsorption capacity when compared to methane. The strong adsorption of CO2 improves the release of natural gas from kerogen pores. This indicates that the separation of produced CO2 will be a minimal cost. Transport in kerogen has significant pore wall effects, and includes large mass fluxes of the adsorbed molecules by the walls due to surface diffusion. In essence, the adsorbed CO2 molecules significantly influence transport of methane. The results also show core-plug permeability is stress-sensitive due to presence of micro-fractures. Forward simulation results using optimum parameters indicate that closure stress developing near the fractures could significantly control the volume of CO2 injected. This raises operational issues on when to start injecting, and how to inject CO2. Using a simulation study of a production well with single-fracture, we show that fracture closure stress develops rapidly and production rate becomes a slave of the fracture geo-mechanics, e.g., strength of the proppants and the level of proppant embedment.
Fluid storage capacity measurements of core-plugs in the laboratory considers pore-volume as a function of effective stress. The latter is equal to (Applied Confining Pressure) − (Effective Stress Coefficient) x (Applied Pore Pressure). However, results are often reported as a function of difference in the applied pressures, because the coefficient is unknown and depends on the sample. This creates confusion during the interpretation of laboratory data and leads to added uncertainties in the analysis of storage capacity.
In this paper we present a new laboratory method that allows simultaneous prediction of the sample pore volume, coefficient of isothermal pore compressibility, and the stress coefficient. These quantities are necessary to predict the fluid storage as a function of effective stress. The method requires two stages of gas (helium) uptake by the sample under confining pressure and pore pressure and measures pressure-volume data. Confining pressure is always kept larger than the equilibrium pore-pressure but their values at each stage are changed arbitrarily. The method considers gas leakage adjustments at high pore pressure. The analysis is simple and includes simultaneous solutions of two algebraic equations including the measured pressure-volume data.
The model is validated by taking the reference pore volume near zero stress. The reference volume predicted matches with that measured independently using the standard helium porosimeter. For sandstone and shale, the pore compressibility is on average 10-5 psi-1 and the effective stress coefficient is slightly higher than 1. The effective stress coefficient in isotropic elastic porous materials is known as the Biot coefficient and the value we predict indicates the relationship between the bulk and grain volume moduli.
Interestingly the effective stress coefficient predicted using shale samples rich in clays and organic matter is slightly higher than for sandstone. This indicates that other features of the sample such as fine-scale texture (laminations, and anisotropy, etc.) could come into play during the fluid storage measurements.
Methane hydrate is formed in a sand pack that undergoes cooling-heating cycles over a range of temperature. Five cycles are designed so that hysteresis can be observed in the sand pack. Each cycle has a different melting temperature which leads to varying intensity of temperature relaxation effect on the hysteresis. Evidence of hysteresis is observed in three separate temperature readings of thermocouples. Formation of hydrates is dependent on the thermal cooling rate of the sand pack, and the melting temperature of the previous cycle. A temperature increase is observed in the whole system, and this increase is driven by temperature peaks indicating significant hydrate formation near the thermocouples. These peaks have important effects on the whole system. By comparing each cycle's temperature peaks, hysteresis is clearly observed at the temperature readings of the short thermocouple. The same hysteresis pattern follows for the location of the temperature peaks. When significant hydrate formation occurs in the sand pack, a steepening of the pressure decline is observed, indicating a rapid loss of free gas in the system. The pattern that is observed in the temperature peaks is also identified in the pressure profiles, thus linking the gas saturation to hydrate formation. The time derivative of pressure corroborates these findings. A new model is proposed for the prediction of secondary hydrate formation time as a function of the melting temperature the porous medium experienced.
Current trends in shale gas industry require an advanced-level understanding of fracturing water invasion into formation and the subsequent water-shale interactions. Previously, we studied osmosis and clay swelling effects on the permeability of the shale formation. Shale, with an average 50% clay content, could hold large cation-exchange-capacity and significantly improved membrane efficiency, which may promote swelling and changes in the stress. In addition, large temperature-gradient effects due to cold water contacting the formation has not been investigated in detail.
A new geomechanically-coupled reservoir flow simulator is developed, which accounts for cold freshwater imbibition, osmosis and clay-swelling effects on the formation permeability under stress. The model includes aqueous and gaseous phases with three components: water, gas and salt. Governing geomechanical equation includes pore-pressure as well as temperature gradients. Volumetric strain (porosity changes) is calculated as a function of the mean normal stress, pore pressure and temperature. Imbibition occurs in water-wet inorganic part of the matrix, in the micro-cracks. Osmosis and clay swelling effects develop when the imbibed water in the micro-cracks interacts with the saline water in clay pores, which acts as a semi-permeable membrane to the water and experiences pore (osmotic) pressure changes and swelling of the clay in the formation.
The effect of temperature is pronounced early during the shut-in when imbibition of cold water takes place rapidly. Cold water introduces a low-stress region near the fracture due to thermal expansion effect and pore pressure buildup. We used a criterion and discuss the potential for fracturing. It is anticipated that the fracturing develops during forced imbibition of cold water given that a large difference exists between the injected water and the formation temperatures.
Seunghwan Baek and I. Yucel Akkutlu, Texas A&M University Summary Source rocks, such as organic-rich shale, consist of a multiscale pore structure that includes pores with sizes down to the nanoscale, contributing to the storage of hydrocarbons. In this study, we observed hydrocarbons in the source rock partition into fluids with significantly varying physical properties across the nanopore-size distribution of the organic matter. This partitioning is a consequence of the multicomponent hydrocarbon mixture stored in the nanopores, exhibiting a significant compositional variation by pore size-- the smaller the pore size, the heavier and more viscous the hydrocarbon mixture becomes. The concept of composition redistribution of the produced fluids uses an equilibrium molecular simulation that considers organic matter to be a graphite membrane in contact with a microcrack that holds bulk-phase produced fluid. A new equation of state (EOS) was proposed to predict the density of the redistributed fluid mixtures in nanopores under the initial reservoir conditions. A new volumetric method was presented to ensure the density variability across the measured pore-size distribution to improve the accuracy of predicting hydrocarbons in place. The approach allowed us to account for the bulk hydrocarbon fluids and the fluids under confinement. Multicomponent fluids with redistributed compositions are capillary condensed in nanopores at the lower end of the pore-size distribution of the matrix ( 10 nm). The nanoconfinement effects are responsible for the condensation. During production and pressure depletion, the remaining hydrocarbons become progressively heavier. Hence, hydrocarbon vaporization and desorption develop at extremely low pressures. Consequently, hydrocarbon recovery from these small pores is characteristically low. Introduction Resource shale and other source-rock formations with significant amounts of organic matter, such as mudstone, siltstone, and carbonate, have a multiscale pore structure that includes fractures, microcracks, and pores down to a few nanometers (Ambrose et al. 2012; Loucks et al. 2012). The total amount of hydrocarbons stored is directly proportional to the amount of organic matter.
Brice Y. Kim and I. Yucel Akkutlu, Texas A&M University, and Vladimir Martysevich and Ronald G. Dusterhoft, Halliburton Summary The stress-dependent permeabilities of split shale core plugs from Eagle Ford, Bakken, and Barnett Formation samples are investigated in the presence of microproppants. An analytical permeability model is developed for the investigation, including the interactions between the fracture walls and monolayer microproppants under stress. The model is then used to analyze a series of pressure-pulsedecay measurements of the propped shale samples in the laboratory. The analysis provides the propped-fracture permeability of the samples and predicts a parameter related to the quality of the proppant areal distribution in the fracture. The proppant-placement quality can be used as a measure of success of the delivery of proppants into microfractures and to design stimulation experiments in the laboratory. Introduction Unconventional-oil/gas resources, such as tight gas/oil and resource shale, have low porosity and ultralow permeability. Creating a well-connected complex fracture network is a key component of increasing the permeability and accelerating production. The early era of hydraulic fracturing horizontal wells in unconventional formations was concerned with achieving long fractures with multistage treatments with large cluster spacing. However, recent trends in this type of well completion and stimulation involve fractures that are created in narrower clusters in much closer spacing, targeting larger surface areas. It is argued that the practice of hydraulic fracturing with narrow clusters in close spacing along a lateral wellbore creates fractures with significantly reduced sizes, but in a complex network (Rassenfoss 2017). The creation of a network of fractures includes major operational issues.
Significant research has been conducted on hydrocarbon fluids in the organic materials of source rocks, such as kerogen and bitumen. However, these studies were limited in scope to simple fluids confined in nanopores, while ignoring the multicomponent effects. Recent studies using hydrocarbon mixtures revealed that compositional variation caused by selective adsorption and nanoconfinement significantly alters the phase equilibrium properties of fluids. One important consequence of this behavior is capillary condensation and the trapping of hydrocarbons in organic nanopores. Pressure depletion produces lighter components, which make up a small fraction of the in-situ fluid. Equilibrium molecular simulation of hydrocarbon mixtures was carried out to show the impact of CO2 injection on the hydrocarbon recovery from organic nanopores. CO2 molecules introduced into the nanopore led to an exchange of molecules and a shift in the phase equilibrium properties of the confined fluid. This exchange had a stripping effect and, in turn, enhanced the hydrocarbon recovery. The CO2 injection, however, was not as effective for heavy hydrocarbons as it was for light components in the mixture. The large molecules left behind after the CO2 injection made up the majority of the residual (trapped) hydrocarbon amount. High injection pressure led to a significant increase in recovery from the organic nanopores, but was not critical for the recovery of the bulk fluid in large pores. Diffusing CO2 into the nanopores and the consequential exchange of molecules were the primary drivers that promoted the recovery, whereas pressure depletion was not effective on the recovery. The results for N2 injection were also recorded for comparison.
Pang, Wei (State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Sinopec Research Institute of Petroleum Engineering) | Akkutlu, I. Yucel (Texas A&M University, College Station) | Ding, Shidong (State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Sinopec Research Institute of Petroleum Engineering) | Zhang, Tongyi (State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Sinopec Research Institute of Petroleum Engineering) | Xia, Wenwu (Harding Shelton Petroleum Engineering & Technology)
Organic matter in source rocks such as coal and shale hold significant amount of adsorbed gas. Laboratory methos are available to measure the gas amount stored in the source rock samples. However, adsorbed gas release from the organic pore network and its production using wells is an issue under debate. The intricacy in the debate is mainly due to the physical properties of the adsorbed phase adsorbed phase. The adsorbed phase has an unknown composition and its molecules released in a selective fashion controlled by the organic pore walls. The organic matter nanopores bring in added complexity to the analysis due to nano-confinement effects. Our objective in this study is to predict the gas composition in kerogen pores in order to gain insight into the compositional variation with the pore size distribution in the formation. This prediction should be done properly at the initial conditions and during the pressure depletion. Thus, we also would like to investigate gas desorption impact on the adsorbed hase composition due to production.
A molecular simulation method is developed using grand canonicalMonte Carlo simulation to study the in-situ composition of natural gas in model matter pores. We used the composition of produced fluid from a Chinese shale gas well. In essence, the method redistributes the fluid composition back into the organic pores at initial reservoir conditions. Then one-by-one the pores are depleted while the compositional variation in the pores is monitored. The recovery is measured by comparing the residual hydrocarbon molecules at different pressure steps during the depletion. The mean free path length of the fluid molecules, the fluid density and viscosity are computed once the thermodynamic simulation reaches an equilibrium.
Water-shale interactions are traditionally perceived as complex phenomena due to reactive nature of shale with water. However, the current trends in shale gas industry requires an advanced-level of understanding of these interactions and their impact on gas production. In this paper we investigate the invasion of fracturing water into the formation and the subsequent water-shale interactions. Objective of this work is to study osmosis and clay swelling effects of the invasion on the formation permeability.
For this purpose, a new geomechanically-coupled reservoir flow simulator is developed, which accounts for water imbibition, osmosis and clay swelling effects on the formation permeability under stress. The simulation model considers the formation has a multi-scale pores consisting of microcracks, clay pores and organic pores. Water imbibition occurs in the water-wet inorganic part of the matrix in the microcracks. Osmosis and clay swelling effects develop in the clay pores acting as semi-permeable membrane to the imbibed water and changing the local stress in the formation. The simulation model includes aqueous and gaseous phases with three components: water, gas and salt.
The simulation results show that the formation permeability is dynamically affected during the shut-in period by a combination of mechanisms including imbibition, capillarity, diffusion/osmosis, and total stress. Notably, a permeability impairment zone, rather a fracture skin, develops near the fracture. The permeability alteration is due to osmosis-related clay swelling and changing stresses in the formation. The magnitude of the permeability alteration is controlled mainly by the salt concentration difference between the fracturing fluid and the clay-bound water, the clay-membrane efficiency, the clay cation exchange capacity (CEC), the clay porosity, the stress and the duration of the shut-in time. We develop a fracture skin factor that can be used with the single-phase (gas) shale reservoir flow simulators that are typically run in the absence of water invasion at the scale of the stimulated reservoir volume (SRV) and in multidimensional geometries.
Currently there is a clear need in the unconventional industry to better-understand and control the hydraulic fracturing fluid-shale interactions. This work is an important milestone considering the complexity of the problem and suggesting that the water chemistry and the formation lithology plays a significant role after the fracturing operations.
Bui, Khoa (Texas A&M University) | Akkutlu, I. Yucel (Texas A&M University) | Zelenev, Andrei S. (Flotek Chemistry LLC) | Hill, W. A. (Flotek Chemistry LLC) | Griman, Christian (Flotek Chemistry LLC) | Boudreaux, Trudy C. (Flotek Chemistry LLC) | Silas, James A. (Flotek Chemistry LLC)
Source rocks contain significant volumes of hydrocarbon fluids trapped in kerogen, however their effective recovery is challenged due to amplified fluid-wall interactions and the nanopore confinement impact on fluid composition. Enhanced oil production can be achieved by modifying the existing molecular forces in kerogen pore-network by using custom-designed targeted chemistry technologies. Our objective is to show how the transport of hydrocarbons in kerogen and its recovery can be altered with the delivery of microemulsion nanodroplets into the pore network. This is done by using computational chemistry and molecular dynamics (MD) simulations.
Molecular dynamics simulation is used to generate a 3D model replica of a Type II kerogen representative of source rocks located in Delaware and Midland basins in the United States. Oil phase saturated kerogen is modeled as consisting of nine different types of molecules: dimethyl naphthalene, toluene, tetradecane, decane, octane, butane, propane, ethane and methane. The delivered microemulsion is an aqueous dispersion of solvent-swollen surfactant micelles. The solvent and nonionic surfactant present in the microemulsion are modeled as d-limonene and dodecanol heptaethyl ether (C12E7), respectively. Molecular dynamics simulation experiments include two steps: (i) the injection of microemulsion treatment fluid into the oil-saturated kerogen pore-network, and (ii) transient flow-back of the oil-chemical mixture in the pore network. The utilized 3D kerogen models were developed based on a representative oil sample composition (H, C, O, S, N) from the region. Simulation results show that microemulsions can affect the reservoir via two different mechanisms. During the injection, microemulsion nanodroplets that enter the nano-capillaries of pore network disperse in the liquid present in the pore space under the influence of pore walls. The solvent dissolves in the oil phase and alters the physical and transport properties of the phase, while the surfactant molecules modify the wettability of the solid kerogen surfaces. The recovery effectiveness of heavier oil fractions is improved compared to the recovery effectiveness achieved with surfactant micelles without the solubilized solvent.
New 3D kerogen models are presented using atomistic modeling and molecular simulations. These models possess important chemical and physical characteristics of the organic matter of the source rock. Molecular dynamic experiments indicate that solubilized solvent and surfactant are delivered as part of a microemulsion droplet and are expected to aid the mobilization of oil present within kerogen.