TOUGHREACT Code Research Articles

Geochemical Modeling of Changes in Storage Rock Environments at CO2 Injection Sites

Geochemical modeling in TOUGHREACT code was used to simulate chemical processes in CO2–rock–brackish water systems in a pilot research environment of CO2 storage in the Brodske area (Czech Republic). Models studied mineralogical changes in rock samples resulting from acidification of the aqueous phase caused by the dissolution of pressurized supercritical CO2. Rock samples of the reservoir horizon and cement from the grouting of an injection borehole were considered, and the water phase represented the mineralized groundwater. The aim of the study was to characterize the influence of CO2 in the geological structure on mineralogical rock changes and to predict gas distribution through the rocks bearing brackish water. The most important chemical processes are dissolution of carbonates and clay minerals during the injection of CO2 into the structure, as the increase in porosity in the structure affects the sequestration capacity of the reservoir rock. In the CO2–cement–brackish water system, the models confirm the rapid dissolution of portlandite and its replacement with calcite. The CSH gel is also dissolved, and silica gel appears. The porosity of the cement decreases. Further studies on such a cement slurry are needed to prevent the possibility of mechanical damage to the integrity of the borehole.

Geochemical Modelling of the Evolution of Caprock Sealing Capacity at the Shenhua CCS Demonstration Project

CO2 geological storage is considered as an important measure to reduce anthropogenic CO2 emissions to the atmosphere for addressing climate change. The key prerequisite for long-term CO2 geological storage is the sealing capacity of caprock. This study investigates the evolution of sealing capacity of caprock induced by geochemical reactions among CO2, water and caprock using TOUGHREACT code based on the Heshanggou Formation mudstone at the Shenhua Carbon Capture and Storage (CCS) demonstration site of China. The results show that the self-sealing phenomenon occurs in the lower part of the caprock dominated by the precipitation of dawsonite, magnesite, siderite, Ca-smectite and illite. While the self-dissolution occurs in the upper part of caprock mainly due to the dissolution of kaolinite, K-feldspar, chlorite and Ca-smectite. Sensitivity analyses indicate that the precipitation of dawsonite, magnesite, siderite is highly advantageous leading to self-sealing of caprock, with albite and chlorite dissolution providing Na+, Mg2+ and Fe2+. The dissolution of K-feldspar dominates illite precipitation by providing required K+, and albite affects Ca-smectite precipitation. The self-sealing and self-dissolution of caprock are enhanced significantly with increasing temperature, while the effect of salinity on caprock sealing capacity is negligible perhaps due to the low salinity level of formation water.

Numerical simulation and feasibility assessment of acid gas injection in a carbonate formation of the Tarim Basin, China

An enormous amount of acid gas, containing carbon dioxide (CO2) and hydrogen sulfide (H2S), is generated in the exploitation of oil and gas reservoirs in the Tarim Basin, China. An appropriate management plan is required to safely dispose of the acid gas, and common strategy considered for the safe disposal of acid gas is the injection of it into deep formations – this strategy mitigates greenhouse gas emissions and avoids costs associated with desulfurization. A feasibility assessment of acid gas injection requires a detailed investigation of the potential physical and geochemical impacts. Reactive transport simulations based on the mineralogical composition and the hydrochemical characteristics of a carbonate formation in the Tarim Basin were conducted to identify the physical and geochemical interactions of acid gas with the mineral matrix and formation water. Acid gas (59% CO2 and 41% H2S) was injected at a constant rate of 19 200 Nm3/d for 25 years, and the simulation was run by the TMVR_EOSG module of the TOUGHREACT code for a period of 10 000 years. The results indicate that the minimum liquid saturation is much larger than the residual water saturation, and the pressure buildup is below the allowable pressure increase. Additionally, the porosity change is found to be negligible due to the small changes in calcite and quartz in the volume fraction. From this perspective, acid gas injection in the carbonate formation of the Tarim Basin seems feasible. Furthermore, the fast breakthrough of CO2 can provide an advanced warning of a potential breakthrough of acid gas. Last, the injection rate can be increased to accelerate acid gas trapping, and the results could be used as guidance for future acid gas injection operations.

2D reactive transport simulations of mid-ocean ridge hydrothermal systems

Water-rock interactions in mid-ocean ridge hydrothermal systems are a critical part of Earth system evolution. Extensive insights have been developed from vent fluid chemistry and laboratory experiments, but these leave unanswered many questions about the temporal evolution and spatial structure of the hydrothermal systems that can only be addressed with reactive transport simulations. Other issues are the effects of changing spreading rates and seawater chemistry through Earth history. We are addressing this problem using the Toughreact code, starting with 2D static (no seafloor spreading) simulations of the near-axis region where most of the interaction occurs. The simulations use a dual-permeability grid to represent fractured rocks, and also have a formulation for Sr isotope exchange. Vent fluid Ca, Mg, SO4, and Na concentrations and Sr isotopes can be used as a guide to fluid chemical evolution. Initial simulations reproduce modern vent fluid chemistry even with maximum temperature only at 380°C, and suggest that fluids need not be in equilibrium with the rocks at any point in the system. Model fluids continue to evolve chemically even in the upflow zone prior to venting. The effects of different seawater chemical composition, as proposed for the Cretaceous, for example, can be captured with charge-balance models.

Reactive transport modelling of hydrothermal dolomitisation using the CSMP++GEM coupled code: Effects of temperature and geological heterogeneity

Reactive transport simulations using our CSMP++GEM coupled code were applied to study the major controls on replacement dolomitisation and the development of dolomite geobodies in a hydrothermal setting. A series of 2D simulations show how elevated temperature and reactive surface area increase the rate of dolomitisation, and result in a dolomite replacement front that is both sharper and inclined at a higher angle from vertical. This inclination, an effect of gravity segregation, is apparent in thick homogeneous units, but in layered systems the lithological contrast determines the shape of the dolomite front. The increase in permeability resulting from porosity generation upon replacement of calcite by dolomite has a major effect on accelerating the overall progress of dolomitisation. In contrast, the changes in fluid density due to chemical reactions and the pressure dependence of thermodynamic data have a minor influence under simulated conditions. Primary dolomite forms slowly after complete replacement of host calcite, leading to porosity decrease, and is only locally important around the source of the hydrothermal fluid.For a simple layered system, our model results are in excellent agreement with those obtained using TOUGHREACT code. They do, however, show the advantage of unstructured triangular over structured rectangular meshes for resolving complex curved/inclined front shapes. Such meshes also offer benefits in simulating fault-controlled hydrothermal dolomitisation.Our simulations predict dolomite geobodies comparable in scale and morphology to natural examples documented at outcrops, and underline the importance of understanding the permeability structure within and around the fault zone.

Reactive transport modeling of long-term CO2 sequestration mechanisms at the Shenhua CCS demonstration project, China

Carbon dioxide injection into deep saline aquifers results in a variety of strongly coupled physical and chemical processes. In this study, reactive transport simulations using a 2-D radial model were performed to investigate the fate of the injected CO2, the effect of CO2-water-rock interactions on mineral alteration, and the long-term CO2 sequestration mechanisms of the Liujiagou Formation sandstone at the Shenhua CCS (carbon capture and storage) pilot site of China. Carbon dioxide was injected at a constant rate of 0.1 Mt/year for 30 years, and the fluid flow and geochemical transport simulation was run for a period of 10 000 years by the TOUGHREACT code according to the underground conditions of the Liujiagou Formation. The results show that different trapping phases of CO2 vary with time. Sensitivity analyses indicate that plagioclase composition and chlorite presence are the most significant determinants of stable carbonate minerals and CO2 mineral trapping capacity. For arkosic arenite in the Liujiagou Formation, CO2 can be immobilized by precipitation of ankerite, magnesite, siderite, dawsonite, and calcite for different mineral compositions, with Ca2+, Mg2+, Fe2+ and Na+ provided by dissolution of calcite, albite (or oligoclase) and chlorite. This study can provide useful insights into the geochemistry of CO2 storage in other arkosic arenite (feldspar rich sandstone) formations at other pilots or target sites.

Dissolution sequestration mechanism of CO2 at the Shiqianfeng saline aquifer in the Ordos Basin, northwestern China

This study focused on the target injection layers of deep saline aquifers in the Shiqianfeng Fm. in the Carbon Capture and Sequestration (CCS) Demonstration Projects in the Ordos Basin, northwestern China. The study employed a combination method of experiments and numerical simulation to investigate the dissolution mechanism and impact factors of CO2 in these saline aquifers. The results showed (1) CO2 solubility in different types of water chemistry were shown in ascending order: MgCl2-type water < CaCl2-type water < Na2SO4-type water < NaCl-type water < Na2CO3-type water < distilled water. These results were consistent with the calculated results undertaken by TOUGHREACT with about 5% margin of error. CO2 solubility of Shiqianfeng Fm. saline was 1.05 mol/L; (2) compared with distilled water, the more complex the water’s chemical composition, the greater the increase in HCO3 −concentration. While the water’s composition was relatively simple, the tested water’s HCO3 −concentrations were in close accord with the calculated value undertaken by the TOUGHREACT code, and the more complex the water’s composition, the poorer the agreement was, probably due to the complex and unstable HCO3 − complicating matters when in an aqueous solution system including both tested HCO3 −concentration and calculated HCO3 −concentration; (3) the CO2 solubility in the saline at the temperature conditions of 55 °C and 70 °C were 1.17 and 1.02 mol/L. When compared with the calculated value of 1.20 and 1.05 mol/L, they were almost the same with only 1 and 3% margin of error; concentrations of HCO3 − were 402.73 mg/L (0.007 mol/L) and 385.65 mg/L (0.006 mol/L), while the simulation results were 132.16 mg/L (0.002 mol/L) and 128.52 mg/L (0.002 mol/L). From the contrast between the tested data and the calculated data undertaken by the TOUGHREACT code, it was shown that TOUGHRACT code could better simulate the interaction between saline and CO2 in the dissolution sequestration capacity. Therefore, TOUGHREACT code could be used for the inter-process prediction of CO2 long-term geological storage of CO2; (4) The Ca2+ concentration and SO4 2−concentration in saline water had less effect on the solubility of CO2 and HCO3 −concentration. In addition, TDS and pH values of saline affected not only the solubility of CO2, but also the conversion of CO2 to HCO3 − due to that they can affect the activity and acid-base balance. So in fact, we just need to consider that the TDS and pH values are main impact factors in the dissolution sequestration capacity of CO2 geological sequestration in deep saline aquifers.

Benefits and restrictions of 2D reactive transport simulations of CO2 and SO2 co-injection into a saline aquifer using TOUGHREACT V3.0-OMP

Many simulation studies on CO2 storage in deep saline aquifers focus on flow transport modelling and pressure development. Studies including geochemical aspects mostly address the acidic impact of pure CO2 injection on the minerals of the reservoir complex. More recent reactive transport simulations respect compositions of a flue gas stream closer to reality, i.e. they include physical or geochemical impacts of impurities within the CO2 stream. Here the common approach is to introduce trace gases into the multidimensional system as dissolved solutes in an additional aquatic phase, injected into the reservoir as brine. The most recent release of version V3.0-OMP of the TOUGHREACT code provides the new feature “Transport of trace gas species in CO2–H2O carrier gas”, allowing for direct injection and transport of trace gases in the CO2 phase. This study addresses the geochemical impact of co-injected SO2 as a CO2 flue gas impurity on the reservoir rock in a generic model, based on parameters of the Heletz saline aquifer. Therefore numerical 2D reactive transport simulations applying the trace gas transport approach as provided by TOUGHREACT V3.0 are performed for a ten year injection period. The simulations predict a distinct inner region of 200m radial distance under the dominating impact of dissolved SO2, while a distance of up to 2000m is influenced by CO2. The region impacted by SO2 is characterised by a distinct ankerite dissolution and coupled precipitation pattern of anhydrite. In the analysis of the results, special emphasis is given to the benefits and restrictions of the trace gas transport approach in comparison to the impurity modelling by injection of additional brine, particularly addressing the topic of ionic strength limitations.

Bio-geochemical reactive transport modeling of microbial induced calcite precipitation to predict the treatment of sand in one-dimensional flow

Microbial induced calcite precipitation (MICP) has been well studied to date in the laboratory as a viable alternative soil improvement technique that harnesses a natural bacterial process to induce cementation. Specifically, MICP utilizes the microbial process of hydrolysis of urea to induce pH increase leading to calcite precipitation. The study presented herein demonstrates the utility of a simple bio-geochemical reactive transport model to predict MICP in one-dimensional column experiments. The mathematical model was originally developed in the framework of the TOUGHREACT code to include kinetically controlled reaction rates for urea hydrolysis and calcite precipitation. Inverse modeling, via UCODE-2005, is utilized to calibrate and verify the model to experimental data including aqueous and mineral chemistry. Results indicate good agreement between data and simulated results for capturing the trends and magnitudes of a variety of MICP treatment schemes in half meter, one-dimensional flow columns. A design procedure is presented for predicting MICP in one-dimensional flow by sequentially coupling UCODE-2005 with TOUGHREACT.

A reactive transport model for geochemical mitigation of CO2 leaking into a confined aquifer

Abstract Long-term storage of anthropogenic CO 2 in the subsurface generally assumes that caprock formations will serve as physical barriers to upward migration of CO 2 . However, as a precaution and to provide assurances to regulators and the public, monitoring is used detect any unexpected leakage from the storage reservoir. If a leak is found, the ability to rapidly deploy mitigation measures is needed. Here we use the TOUGHREACT code to develop a series of two-dimensional reactive transport simulations of the hydrogeochemical characteristics of a newly formed CO 2 leak into an overlying aquifer. Using this model, we consider: (1) geochemical shifts in formation water indicative of a leak; (2) hydrodynamics of pumping wells in the vicinity of a leak; and (3) delivery of a sealant to a leak through an adjacent well bore. Our results demonstrate that characteristic shifts in pH and dissolved inorganic carbon can be detected in the aquifer prior to the breakthrough of supercritical CO 2 , and could offer a potential means of identifying small and newly formed leaks. Pumping water into the aquifer in the vicinity of the leak provides a hydrodynamic control that can temporarily mitigate the flux rate of CO 2 and facilitate delivery of a sealant to the location of the caprock defect. Injection of a fluid-phase sealant through the pumping well is demonstrated by introduction of a silica-bearing alkaline flood, resulting in precipitation of amorphous silica in areas of neutral to acidic pH. Results show that a decrease in permeability of several orders of magnitude can be achieved with a high molar volume sealant, such that CO 2 flux rate is decreased. However, individual simulation results are highly contingent upon both the properties of the sealant, the porosity-permeability relationship employed in the model, and the relative flux rates of CO 2 and alkaline flood introduced into the aquifer. These conclusions highlight the need for both experimental data and controlled field tests to constrain modelling predictions.

Modelling radionuclide transport in large fractured-media systems: the example of Forsmark, Sweden

The planned high-level nuclear waste repository at Forsmark, Sweden, will accommodate 6,824 containers with a total of 13,920 tonnes of uranium in burnt fuel at approximately 400 m depth in a fractured-granite aquifer. The transport of radionuclides, which may be released from the disposed waste, is simulated with the TOUGHREACT code for a three-dimensional model with 305,571 elements. The model performs coupled flow-transport simulations. It aims to achieve more realistic simulations of contaminant transport than the commonly used decoupled procedure consisting of three-dimensional flow and one-dimensional transport simulations. The model has a relatively small problem size because it is designed as a double-porosity model (one matrix continuum) that is the parameterised equivalent of a much larger multiple-interacting continua (MINC) model, i.e. a model with a finely discretised matrix (several matrix continua). The parameterisation is performed with two-dimensional models. Only one or two variables among three variables (diffusive transport distance between fracture and matrix, retardation factor and effective diffusivity) have to be parameterised. The results obtained with the parameterised three-dimensional model are very close to those that can be obtained with a much larger MINC model but may be quite different from those that can be obtained with the conventional decoupled procedure.

Chemical Evolution of Bentonite Buffer in a Final Repository of Spent Nuclear Fuel During the Thermal Phase

Finnish spent nuclear fuel final disposal is planned to be based on the Kärnbränslesäkerhet 3-Vertical concept, which was originally planned for fractured crystalline bedrock. Within this concept, the role of the bentonite buffer is considered central. The aim of the study was to model the evolution of the final repository during the thermal phase (heat-generating period of spent fuel) when the bentonite is initially only partially saturated. There is an essential need to determine how temperature influences saturation and how both of these factors affect the chemistry of bentonite.In this study the Long-Term Test of Buffer Materials A2 parcel test at the Äspö hard rock laboratory in Sweden was modeled using TOUGHREACT code. The results focused on the following phenomena occurring in the bentonite: cation exchange, changes of bentonite pore water, mineral alterations, saturation, and pressure changes in bentonite buffer.The results show similarity with experimental data. However, the results are open to questions, and further study is needed to confirm the validity of the results. Differences between modeled and experimental results can be explained, for example, so that the experimental results are not from the fracture position as our one-dimensional model assumes.

Application of numerical modelling to a case of compaction-driven dolomitization: a Jurassic palaeohigh in the Po Plain, Italy

Dolomitization of a carbonate platform can occur at different times and in different diagenetic environments, from synsedimentary to deep burial settings. Numerical simulations are valuable tools to test and select the model that, among different hypotheses compatible with field and geochemical data, best honour mass balance, kinetic and thermodynamic constraints. Moreover, the simulation can predict the distribution of the dolomitized bodies in the subsurface and evaluate porosity changes; valuable information for the oil industry. This study is the first attempt to reproduce and investigate the compaction dolomitization model. The diagenetic study of the Jurassic carbonate basin and palaeohigh system of the Po Plain indicates that the carbonates of the palaeohighs were dolomitized by basin compaction fluids. The main goal of the simulations is to evaluate the origin and evolution of the dolomitizing fluids and to provide insights regarding the distribution of the potential reservoir-dolomitized bodies in the Po Plain. The modelling process is subdivided into two steps: basin modelling and reactive transport modelling. The SEBE3 basin simulator (Eni proprietary) was used to create a three-dimensional model of the compacting system. The results include compaction fluid flow rate from the basin to the palaeohigh, compaction duration and a determination of the total amount of fluid introduced into the palaeohigh. These data are then used to perform reactive transport modelling with the TOUGHREACT code. Sensitivities on dolomite kinetic parameters suggest that dolomitization was an efficient process even at low temperatures, with differences mainly related to the dynamics of the process. Fluid composition is one of the main constraints, the sea water derived compaction fluid is proven to be efficient for dolomitization due to its relatively high Mg content. Simulations also confirmed that permeability is the most important factor influencing fluid flow and, consequently, the dolomite distribution in the formation. Permeable fractured zones have a strong influence, diverting the dolomitizing fluids from their normal path towards overlying or lateral zones. Moreover, the simulations showed that, after dolomite replacement is complete, the dolomitizing fluids can precipitate dolomite cement, causing over-dolomitization, with related localized plugging effects in the zone of influx. Mass balance calculations indicate that in the dolomitization compaction model, the amount of compaction water fluxed from the basin to the carbonate is the main constraint on dolomitization efficiency. This observation implies that the ratio between the volume of the basin undergoing compaction and the volume of the palaeohigh is a limiting factor on the final size of the dolomitized bodies. An isolated palaeohigh could be an ideal site for pervasive replacement dolomitization due to the large volume of compaction fluids available compared with the carbonate rock volume. In the case of large platforms, the more permeable margin lithofacies are the most likely sites for compaction model dolomitization. The combined use of a basin simulator and reactive transport modelling has proved to be a successful method to verify model reliability and it provides insights into the volumetric distribution of diagenetic products.