CO2SINK—From site characterisation and risk assessment to monitoring and verification: One year of operational experience with the field laboratory for CO2 storage at Ketzin, Germany

The CO₂SINK pilot project at Ketzin is aimed at a better understanding of geological CO₂ storage operation in a saline aquifer. The reservoir consists of fluvial deposits with average permeability ranging between 50 and 100 mDarcy. The main focus of CO₂SINK is developing and testing of monitoring and verification technologies. All wells, one for injection and two for observation, are equipped with smart casings (sensors behind casing, facing the rocks) containing a Distributed Temperature Sensing (DTS) and electrodes for Electrical Resistivity Tomography (ERT). The in-hole Gas Membrane Sensors (GMS) observed the arrival of tracers and CO₂ with high temporal resolution. Geophysical monitoring includes Moving Source Profiling (MSP), Vertical Seismic Profiling (VSP), crosshole, star and 4-D seismic experiments. Numerical models are benchmarked via the monitoring results indicating a sufficient match between observation and prediction, at least for the arrival of CO₂ at the first observation well. Downhole samples of brine showed changes in the fluid composition and biocenosis. First monitoring results indicate anisotropic flow of CO₂ coinciding with the “on-time” arrival of CO₂ at observation well one (Ktzi 200) and the later arrival at observation well two (Ktzi 202). A risk assessment was performed prior to the start of injection. After one year of operations about 18,000 t of CO₂ were injected safely.     

The impact of heterogeneity on the distribution of CO2: Numerical simulation of CO2 storage at Ketzin

Numerical modelling of multiphase flow is an essential tool to ensure the viability of long-term and safe CO₂ storage in geological formations. Uncertainties arising from the heterogeneity of the formation and lack of knowledge of formation properties need to be assessed in order to create a model that can reproduce the data available from monitoring. In this study, we investigated the impact of unknown spatial variability in the petrophysical properties within a sandy channel facies of a fluviatile storage formation using stochastic methods in a Monte Carlo approach. The stochastic method has been applied to the Ketzin test site (CO₂SINK), and demonstrates that the deterministic homogeneous model satisfactorily predicts the first CO₂ arrival time at the Ketzin site. The equivalent permeability was adjusted to the injection pressure and is in good agreement with the hydraulic test. It has been shown that with increasing small-scale heterogeneity, the sharpness of the CO₂ front decreases and a greater volume of the reservoir is affected, which is also seen in an increased amount of dissolved CO₂. Increased anisotropy creates fingering effects, which result in higher probabilities for earlier arrival times. Generally, injectivity decreases with increasing heterogeneity.     

Modelling of CO2 arrival time at Ketzin – Part I

The injection of CO₂ at the Ketzin storage site and the chemical detection of its arrival in the observation well allowed testing of different numerical simulation codes. ECLIPSE 100 (E100, black-oil simulator), ECLIPSE 300 (E300, compositional CO₂STORE) and MUFTE-UG were used for predictive modelling applying a constant injection rate of 1 kg s^?1 CO₂ and for a history match applying the actual variable injection rate which ranged from 0 to 0.7 kg s^?1 and averaged 0.23 kg s^?1. The geological model applied, is based on all available geophysical and geological information and has been the same for all programs.The results of the constant injection regime show a good agreement among the programs with a discrepancy of 21–33% for the CO₂ arrival times. However, it is determined from the comparison of the cumulative mass of CO₂ at the time of CO₂ arrival that the injection regime is an important factor for the accurate prediction of CO₂ migration within a saline aquifer. Comparing the actual variable injection regime with the simulations applying a constant injection rate the results are relatively inaccurate.Regarding the actual variable injection regime, which was evaluated using all three simulators, the computational results show a good agreement with the data actually measured at the first observation well. Here, the calculated arrival times exceeded the actual ones by 8.1% (E100), 9.2% (E300) and 17.7% (MUFTE-UG).It can be concluded that irrespective of the deviations of the simulations, due to combinations of different codes and slight differences in input parameters, all three programs are well equipped to give a reliable estimate of the arrival of CO₂. Deviations in the results mainly occur due to different input data and grid size choices done by the different modelling teams working independently of each other. Deviations of the simulations results compared to the actual CO₂ arrival time result from uncertainties in the implementation of the geological model, which was set up based on well log data and analogue studies.     

Re-establishment of the proper injectivity of the CO2-injection well Ktzi 201 in Ketzin, Germany

The onshore CO₂-storage site Ketzin consists of one CO₂-injection well and two observation wells. Hydraulic tests revealed permeabilities between 50 and 100 mD for the sandstone rock units. The designated injection well Ktzi 201 showed similar production permeability. After installation of the CO₂-injection string, an injection test with water yielded a significantly lower injectivity of 0.002 m³/d kPa, while the observation wells showed an injection permeability in the same range as the productivity. Several possible reasons for the severe decline in injectivity are discussed. Acidification of the reservoir interval, injection at high wellhead pressure, controlled mini-fractures and back-production of the well are discussed to remove the plugging material to re-establish the required injectivity of the well. It has been decided to perform a nitrogen lift and analyse the back-produced fluids. Initially during the lift, the back-produced fluids were dark-black. Chemical and XRD analyses proved that the black solids consisted mainly of iron sulphide. Sulphate-reducing bacteria (SRB) were detected in fluid samples with up to 10⁶ cells/ml by fluorescent in situ hybridisation (FISH) indicating that the formation of iron sulphide was caused by bacterial activity. Organic compounds within the drilling mud and other technical fluids were likely left during the well completion process, thus providing the energy source for strong proliferation of bacteria. During the lift, the fraction of SRB in the whole bacterial community decreased from approximately 32% in downhole samples to less than 5%. The lift of Ktzi 201 succeeded in the full restoration of the well productivity and injectivity. Additionally, the likely energy source of the SRB was largely removed by the lifting, thus ensuring the long-term preservation of the injectivity.     

Petrophysical analysis to investigate the effects of carbon dioxide storage in a subsurface saline aquifer at Ketzin, Germany (CO2SINK)

To test the injection behaviour of CO₂ into brine-saturated rock and to evaluate the dependence of geophysical properties on CO₂ injection, flow and exposure experiments with brine and CO₂ were performed on sandstone samples of the Stuttgart Formation representing potential reservoir rocks for CO₂ storage. The sandstone samples studied are generally fine-grained with porosities between 17 and 32% and permeabilities between 1 and 100 mD.Additional batch experiments were performed to predict the long-term behaviour of geological CO₂ storage. Reservoir rock samples were exposed over a period of several months to CO₂-saturated reservoir fluid in high-pressure vessels under in situ temperature and pressure conditions. Petrophysical parameters, porosity and the pore radius distribution were investigated before and after the experiments by NMR (Nuclear Magnetic Resonance) relaxation and mercury injection. Most of the NMR measurements of the tested samples showed a slight increase of porosity and a higher proportion of large pores.     

Methodology for CO2 chain analysis

The paper presents a methodology for CO₂ chain analysis with particular focus on the impact of technology development on the total system economy. The methodology includes the whole CO₂ chain; CO₂ source, CO₂ capture, transport and storage in aquifers or in oil reservoirs for enhanced oil recovery. It aims at supporting the identification of feasible solutions and assisting the selection of the most cost-effective options for carbon capture and storage. To demonstrate the applicability of the methodology a case study has been carried out to illustrate the possible impact of technology improvements and market development. The case study confirms that the CO₂-quota price to a large extent influence the project economy and dominates over potential technology improvements. To be economic feasible, the studied chains injecting the CO₂ in oil reservoirs for increased oil production require a CO₂-quota price in the range of 20–27 €/tonne CO₂, depending on the technology breakthrough. For the chains based on CO₂ storage in saline aquifers, the corresponding CO₂-quota price varies up to about 40 €/tonne CO₂.     

Model prediction on the rise of pCO2 in uniform flows by leakage of CO2 purposefully stored under the seabed

A numerical study was conducted to predict pCO₂ change in the ocean on a continental shelf by the leakage of CO₂, which is originally stored in the aquifer under the seabed, in the case that a large fault connects the CO₂ reservoir and the seabed by an earthquake or other diastrophism. The leakage rate was set to be 6.025 × 10⁻⁴ kg/m²/sec from 2 m × 100 m fault band, which corresponds to 3800 t-CO₂/year, referring to the monitored seepage rate from an existing EOR field. The target space in this study was limited to the ocean above the seabed, the depth of which was 200 or 500 m. The computational domain was idealistically rectangular with the seabed fault-band perpendicular to the uniform flow. The CO₂ takes a form of bubbles or droplets, depending on the depth of water, and their behaviour and dissolution were numerically simulated during their rise in seawater flow. The advection–diffusion of dissolved CO₂ was also simulated. As a result, it was suggested that the leaked CO₂ droplets/bubbles all dissolve in the seawater before spouting up to the atmosphere, and that the increase in pCO₂ in the seawater was smaller than 500 μ atm.     

Pipeline design for a least-cost router application for CO2 transport in the CO2 sequestration cycle

CO₂ capture and geological storage (CCS) is considered as a viable option to mitigate greenhouse gas emissions during the transition phase towards the use of clean and renewable energy. This paper concentrates on the transport of CO₂ between source (CO₂ capture at plants) and sink (geological storage reservoirs). In the cost estimation of CO₂ transport, the pipeline diameter plays an important role. In this respect, the paper reviews equations that were used in several reports on CO₂ pipeline transport. As some parameters are not taken into account in these equations, alternative formulas are proposed which calculate the proper inner diameter size based on flow rate, pressure drop per unit length, CO₂ density, CO₂ viscosity, pipeline material roughness and topographic height differences (the Darcy–Weisbach solution) and, in addition, on the amount and type of bends (the Manning solution). Comparison between calculated diameters using the reviewed and the proposed equations demonstrate the important influence of elevation difference (which is not considered in the reviewed equations) and pipeline material roughness-related factor on the calculated diameter. Concerning the latter, it is suggested that a Darcy–Weisbach roughness height of 0.045 mm better corresponds to a Manning factor of 0.009 than higher Manning values previously proposed in literature. Comparison with the actual diameter of the Weyburn pipeline confirms the accuracy of the proposed equations. Comparison with other existing CO₂ pipelines (without pressure information) indicate that the pipelines are designed for lower pressure gradients than 25 Pa/m or for (future) higher flow rates. The proposed Manning equation is implemented in an economic least-cost route planner in order to obtain the best economic solution for pipeline trajectory and corresponding diameter.     

Scenario simulations of CO2 injection feasibility, plume migration and storage in a saline aquifer, Scania, Sweden

Deep saline aquifers have large capacity for geological CO₂ storage, but are generally not as well characterized as petroleum reservoirs. We here aim at quantifying effects of uncertain hydraulic parameters and uncertain stratigraphy on CO₂ injectivity and migration, and provide a first feasibility study of pilot-scale CO₂ injection into a multilayered saline aquifer system in southwest Scania, Sweden. Four main scenarios are developed, corresponding to different possible interpretations of available site data. Simulation results show that, on the one hand, stratigraphic uncertainty (presence/absence of a thin mudstone/claystone layer above the target storage formation) leads to large differences in predicted CO₂ storage in the target formation at the end of the test (ranging between 11% and 98% of injected CO₂ remaining), whereas other parameter uncertainty (in formation and cap rock permeabilities) has small impact. On the other hand, the latter has large impact on predicted injectivity, on which stratigraphic uncertainty has small impact. Salt precipitation at the border of the target storage formation affects CO₂ injectivity for all considered scenarios and injection rates. At low injection rates, salt is deposited also within the formation, considerably reducing its availability for CO₂ storage.     

CO2 transportation for carbon capture and storage: Sublimation of carbon dioxide from a dry ice bank

Climate change is being caused by greenhouse gases such as carbon dioxide (CO₂). Carbon capture and storage (CCS) is of interest to the scientific community as one way of achieving significant global reductions of atmospheric CO₂ emissions in the medium term. CO₂ would be captured from large stationary sources such as power plants and transported via pipelines under high pressure conditions to underground storage. If a downward leakage from a surface transportation system module occurs, the CO₂ would undergo a large temperature reduction and form a bank of “dry ice” on the ground surface; the sublimation of the gas from this bank represents an area source term for subsequent atmospheric dispersion, with an emission rate dependent on the energy balance at the bank surface. Gaseous CO₂ is denser than air and tends to remain close to the surface; it is an asphyxiant, a cerebral vasodilator and at high concentrations causes rapid circulatory insufficiency leading to coma and death. Hence a subliming bank of dry ice represents safety hazard. A model is presented for evaluating the energy balance and sublimation rate at the surface of a solid frozen CO₂ bank under different environmental conditions. The results suggest that subliming gas behaves as a proper dense gas (i.e. it remains close to the ground surface) only for low ambient wind speeds.     

Laboratory calibration of the seismo-acoustic response of CO2 saturated sandstones

Ultrasonic experiments were undertaken on CO₂ flooded sandstone core samples, both synthetic sandstones and core plugs from the CRC1 CO₂ injection well in the Otway Basin, Victoria, South Eastern. Australia. The aim of these laboratory tests was to investigate the effects of CO₂ as a pore fluid on the seismo-acoustic response of the sandstone and ultimately to provide an indication of the sensitivity of time-lapse seismic imaging of the eventual CO₂/CH₄ plume in the Otway, Waarre C formation.The synthetic sandstones were manufactured using both a proprietary calcium in situ precipitation (CIPS) process and a silica cementing technique. Samples were tested in a computer controlled triaxial pressure cell where pore pressures can be controlled independently of the confining pressures. The pressure cell is equipped with ultrasonic transducers housed in the loading platens. Consequently, effective pressures equivalent to those expected in the reservoir can be applied while ultrasonic testing is undertaken. Both compressional, P and shear waves, S were recorded via a digital oscilloscope at a range of effective pressure steps. Pore pressures were varied from 4 MPa to 17 MPa to represent both the gaseous and liquid phase regions of the CO₂ phase diagram. Similar experiments were conducted on core plugs from the Waarre C reservoir horizon obtained from the CRC1 injection well, but with an intervening brine-saturated step and in some cases with a CO₂/CH₄ mix of 80%/20% molar fraction which is representative of the field situation. However, the pore pressure in these experiments was held at 4 MPa. Finally, acoustic impedances and reflection coefficients were calculated for the reservoir using Gassmann theory and the implications for imaging the CO₂ plume is discussed.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Dynamis CO2 quality recommendations

In the carbon capture and storage (CCS) chain, transport and storage set different requirements for the composition of the gas stream mainly containing carbon dioxide (CO₂). Currently, there is a lack of standards to define the required quality for CO₂ pipelines. This study investigates and recommends likely maximum allowable concentrations of impurities in the CO₂ for safe transportation in pipelines. The focus is on CO₂ streams from pre-combustion processes. Among the issues addressed are safety and toxicity limits, compression work, hydrate formation, corrosion and free water formation, including the cross-effect of H₂S and H₂O and of H₂O and CH₄.     

Legal and regulatory challenges in the implementation of CO2 geological storage: An Alberta and Canadian perspective

Alberta is the province with the largest CO₂ emissions in Canada, with approximately two-thirds of emissions originating from large stationary sources. Due to the fortuitous association of large CO₂ sources with the storage capacity offered by the underlying Alberta basin, it is expected that large-scale CO₂ geological storage in Canada will occur in Alberta first, and both levels of governments are contemplating measures to facilitate implementation. A review of the current provincial and federal legislation and regulations presented in this paper indicates that the existing legal and regulatory regime is reasonably sufficient, with some modifications, to accommodate the active injection phase of CO₂ capture and storage (CCS) operations, and the early takers of this new technology. However, governments in Alberta and Canada, and likely everywhere, need to address several pressing issues dealing mainly with the CCS post-operational phase. These issues, reviewed in this paper from an Alberta and Canadian perspective, fall into several categories: jurisdictional, property (ownership), regulatory and liability. Because Alberta is a landlocked province, matters relating to CO₂ storage under the seabed will not be addressed here except when discussing matters of jurisdiction and CO₂ classification. Possible models for post-injection liability transfer to the state are also presented. Although this review is focused on western Canada conditions, the issues are broad enough to be of interest in other jurisdictions, which may also adopt parts of the legal and regulatory framework that is quite well developed in Alberta.     

Monitoring of the microbial community composition in saline aquifers during CO2 storage by fluorescence in situ hybridisation

This study reveals the first analyses of the composition and activity of the microbial community of a saline CO₂ storage aquifer. Microbial monitoring during CO₂ injection has been reported. By using fluorescence in situ hybridisation (FISH), we have shown that the microbial community was strongly influenced by the CO₂ injection. Before CO₂ arrival, up to 6 × 10⁶ cells ml⁻¹ were detected by DAPI staining at a depth of 647 m below the surface. The microbial community was dominated by the domain Bacteria that represented approximately 60% to 90% of the total cell number, with Proteobacteria and Firmicutes as the most abundant phyla comprising up to 47% and 45% of the entire population, respectively. Both the total cell counts as well as the counts of the specific physiological groups revealed quantitative and qualitative changes after CO₂ arrival. Our study revealed temporal outcompetition of sulphate-reducing bacteria by methanogenic archaea. In addition, an enhanced activity of the microbial population after five months CO₂ storage indicated that the bacterial community was able to adapt to the extreme conditions of the deep biosphere and to the extreme changes of these atypical conditions.     

Power generation with CO2 capture: Technology for CO2 purification

The goal of this paper is to find methodologies for removing a selection of impurities (H₂O, O₂, Ar, N₂, SO_x and NO_x) from CO₂ present in the flue gas of two oxy-combustion power plants fired with either natural gas (467 MW) or pulverized fuel (596 MW). The resulting purified stream, containing mainly CO₂, is assumed to be stored in an aquifer or utilized for enhanced oil recovery (EOR) purposes. Focus has been given to power cycle efficiency i.e.: work and heat requirements for the purification process, CO₂ purity and recovery factor (kg of CO₂ that is sent to storage per kg of CO₂ in the flue gas). Two different methodologies (here called Case I and Case II) for flue gas purification have been developed, both based on phase separation using simple flash units (Case I) or a distillation column (Case II). In both cases purified flue gas is liquefied and its pressure brought to 110 atm prior to storage.Case I: A simple flue gas separation takes place by means of two flash units integrated in the CO₂ compression process. Heat in the process is removed by evaporating the purified liquid CO₂ streams coming out from both flashes. Case I shows a good performance when dealing with flue gases with low concentration of impurities. CO₂ fraction after purification is over 96% with a CO₂ recovery factor of 96.2% for the NG-fired flue gas and 88.1% for the PF-fired flue gas. Impurities removal together with flue gas compression and liquefaction reduces power plant output of 4.8% for the NG-fired flue gas and 11.6% for the PF-fired flue gas. The total amount of work requirement per kg stored CO₂ is 453 kJ for the NG-fired flue gas and 586 kJ for the PF-fired flue gas.Case II: Impurities are removed from the flue gas in a distillation column. Two refrigeration loops (ethane and propane) have been used in order to partially liquefy the flue gas and for heat removal from a partial condenser. Case II can remove higher amounts of impurities than Case I. CO₂ purity prior to storage is over 99%; CO₂ recovery factor is somewhat lower than in Case I: 95.4% for the NG-fired flue gas and 86.9% for the PF-fired flue gas, reduction in the power plant output is similar to Case I.Due to the lower CO₂ recovery factor the total amount of work per kg stored CO₂ is somewhat higher for Case II: 457 kJ for the NG-fired flue gas and 603 kJ for the PF-fired flue gas.     

Dissolution of a CO2 lake, modeled by using an advanced vertical turbulence mixing scheme

The dissolution of CO₂ from a CO₂ lake with and without a hydrate layer, located at a flat bottom at 3000 m depth has been modeled using the MIT General Circulation Model coupled with the General Ocean Turbulence Model (GOTM). The vertical turbulent mixing scheme takes into account density effects and should give more realistic results for the CO₂ plume than previously used constant eddy diffusivity models. The introduction of a third direction gives qualitatively different results for the spreading of the CO₂ plume than previous 2D results. The dissolution rate and near field dissolved CO₂ concentrations approach a steady state for a given far field ocean current within less than a day. The dissolution rate is highly dependent on the velocity of the ambient current and is reduced with 1.6 when a hydrate layer is introduced.     

Screening and selection of sites for CO2 sequestration based on pressure buildup

This paper presents a simple methodology for estimating pressure pressure buildup due to the injection of supercritical CO₂into a saline formation, and the limiting pressure at which the formation starts to fracture. Pressure buildup is calculated using the approximate solution of Mathias et al. [Mathias, S.A., Hardisty, P.E., Trudell, M.R., Zimmerman, R.W., 2009. Approximate solutions for pressure buildup during CO₂ injection in brine aquifers. Transp. Porous Media. doi:10.1007/s11242-008-9316-7], which accounts for two-phase Forchheimer flow (of supercritical CO₂ and brine) in a compressible porous medium. Compressibility of the rock formation and both fluid phases are also accounted for. Injection pressure is assumed to be limited by the pressure required to fracture the rock formation. Fracture development is assumed to occur when pore pressures exceed the minimum principal stress, which in turn is related to the Poisson’s ratio of the rock formation. Detailed guidance is also offered concerning the estimation of viscosity, density and compressibility for the brine and CO₂. Example calculations are presented in the context of data from the Plains CO₂ Reduction (PCOR) Partnership. Such a methodology will be useful for screening analysis of potential CO₂ injection sites to identify which are worthy of further investigation.     

Comparison of several packings for CO2 chemical absorption in a packed column

CO₂ capture and storage has gained widespread attention as an option for reducing greenhouse gas emissions. Chemical absorption and stripping of CO₂ with hot potassium carbonate (K₂CO₃) solutions has been used in the past, however potassium carbonate solutions have a low CO₂ absorption efficiency. Various techniques can be used to improve the absorption efficiency of this system with one option being the addition of promoters to the solvent and another option being an improvement in the mass transfer efficiency of the equipment. This study has focused on improving the efficiency of the packed column by replacing traditional packings with newer types of packing which have been shown to have enhanced mass transfer performance. Three different packings (Super Mini Rings (SMRs), Pall Rings and Mellapak) have been studied under atmospheric conditions in a laboratory scale column for CO₂ absorption using a 30 wt% K₂CO₃ solution. It was found that SMR packing resulted in a mass transfer coefficient approximately 20% and 30% higher than that of Mellapak and Pall Rings, respectively. Therefore, the height of packed column with SMR packing would be substantially lower than with Pall Rings or Mellapak. Meanwhile, the pressure drop using SMR was comparable to other packings while the gas flooding velocity was higher when the liquid load was above 25 kg m⁻² s⁻¹. Correlations for predicting flooding gas velocities and pressure drop were fitted to the experimental data, allowing the relevant parameters to be estimated for use in later design.