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.     

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.     

Highly siliceous MCM-48 from rice husk ash for CO2 adsorption

Mesoporous MCM-48 silica was synthesized using a cationic-neutral surfactant mixture as the structure-directing template and rice husk ash (RHA) as the silica source. The MCM-48 samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption and SEM. X-ray diffraction pattern of the resulting MCM-48 revealed typical pattern of cubic Ia3d mesophase. BET results showed the MCM-48 to have a surface area of 1024 m²/g and FT-IR revealed a silanol functional group at about 3460 cm⁻¹. Breakthrough experiments in the presence of MCM-48 were also carried out to test the material's CO₂ adsorption capacity. The breakthrough time for CO₂ was found to decrease as the temperature increased from 298 K to 348 K. The steep slopes observed shows the CO₂ adsorption occurred very quickly, with only a minimal mass transfer effect and very fast kinetics. In addition, amine grafted MCM-48, APTS-MCM-48 (RHA), was prepared with the 3-aminopropyltriethoxysilane (APTS) to investigate the effect of amine functional group in CO₂ separation. An order of magnitude higher CO₂ adsorption capacity was obtained in the presence of APTS-MCM-48 (RHA) compared to that with MCM-48 (RHA). These results suggest that MCM-48 synthesized from rice husk ash could be usefully applied for CO₂ removal.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

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.     

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.     

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.     

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.     

Numerical investigation concerning the impact of CO2 geologic storage on regional groundwater flow

Large-scale storage of carbon dioxide in saline aquifers may cause considerable pressure perturbation and brine migration in deep rock formations, which may have a significant influence on the regional groundwater system. With the help of parallel computing techniques, we conducted a comprehensive, large-scale numerical simulation of CO₂ geologic storage that predicts not only CO₂ migration, but also its impact on regional groundwater flow. As a case study, a hypothetical industrial-scale CO₂ injection in Tokyo Bay, which is surrounded by the most heavily industrialized area in Japan, was considered, and the impact of CO₂ injection on near-surface aquifers was investigated, assuming relatively high seal-layer permeability (higher than 10 microdarcy). A regional hydrogeological model with an area of about 60 km × 70 km around Tokyo Bay was discretized into about 10 million gridblocks. To solve the high-resolution model efficiently, we used a parallelized multiphase flow simulator TOUGH2-MP/ECO2N on a world-class high performance supercomputer in Japan, the Earth Simulator. In this simulation, CO₂ was injected into a storage aquifer at about 1 km depth under Tokyo Bay from 10 wells, at a total rate of 10 million tons/year for 100 years. Through the model, we can examine regional groundwater pressure buildup and groundwater migration to the land surface. The results suggest that even if containment of CO₂ plume is ensured, pressure buildup on the order of a few bars can occur in the shallow confined aquifers over extensive regions, including urban inlands.     

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.     

A model for the CO2 capture potential

Global warming is a result of increasing anthropogenic CO₂ emissions, and the consequences will be dramatic climate changes if no action is taken. One of the main global challenges in the years to come is therefore to reduce the CO₂ emissions.Increasing energy efficiency and a transition to renewable energy as the major energy source can reduce CO₂ emissions, but such measures can only lead to significant emission reductions in the long-term. Carbon capture and storage (CCS) is a promising technological option for reducing CO₂ emissions on a shorter time scale.A model to calculate the CO₂ capture potential has been developed, and it is estimated that 25 billion tonnes CO₂ can be captured and stored within the EU by 2050. Globally, 236 billion tonnes CO₂ can be captured and stored by 2050. The calculations indicate that wide implementation of CCS can reduce CO₂ emissions by 54% in the EU and 33% globally in 2050 compared to emission levels today.Such a reduction in emissions is not sufficient to stabilize the climate. Therefore, the strategy to achieve the necessary CO₂ emissions reductions must be a combination of (1) increasing energy efficiency, (2) switching from fossil fuel to renewable energy sources, and (3) wide implementation of CCS.     

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.     

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.     

Numerical parametric study on CO2 capture by indirect thermal swing adsorption

Post-combustion CO₂ capture remains one of the most-challenging issue to lower CO₂ emissions of existing power plants or heavy industry installations because of strong economy and energy efficiency aspects. The major issue comes from CO₂ dilution (4% for NGCC and 14% for PC) and the high flow rates to be treated. Furthermore, CO₂ purity has to be higher than 95% with recovery at 90%, to match the transportation/injection requirements.The MEA absorption process remains the reference today but its energy consumption (about 3 MJ/kg_CO2) and the amine consumption are still challenging drawbacks.The interest of CO₂ capture by indirect TSA (Temperature Swing Adsorption) was demonstrated experimentally in a previous work. The aim of this paper is to present the results of a numerical parametric study. Two main parameters are explored: the desorption temperature (100–200 °C) and the purge flow rate (0.1–0.5 Ndm³ min⁻¹). Four performance indicators are evaluated: CO₂ purity, recovery, productivity and specific energy consumption.Results show that purity above 95% can be achieved. Keeping the 95% target, it is possible to achieve recovery at 81% with productivity at 57.7 g_CO2/kg_ads h and a specific energy consumption of 3.23 MJ/kg_CO2, which is less than for the reference MEA process.Comparison with other adsorption processes exhibits that this process has good potential especially since some improvements are still expected from further research.     

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.     

A method for quick assessment of CO2 storage capacity in closed and semi-closed saline formations

Saline aquifers of high permeability bounded by overlying/underlying seals may be surrounded laterally by low-permeability zones, possibly caused by natural heterogeneity and/or faulting. Carbon dioxide (CO₂) injection into and storage in such “closed” systems with impervious seals, or “semi-closed” systems with non-ideal (low permeability) seals, is different from that in “open” systems, from which the displaced brine can easily escape laterally. In closed or semi-closed systems, the pressure buildup caused by continuous industrial-scale CO₂ injection may have a limiting effect on CO₂ storage capacity, because geomechanical damage caused by overpressure needs to be avoided. In this research, a simple analytical method was developed for the quick assessment of the CO₂ storage capacity in such closed and semi-closed systems. This quick-assessment method is based on the fact that native brine (of an equivalent volume) displaced by the cumulative injected CO₂ occupies additional pore volume within the storage formation and the seals, provided by pore and brine compressibility in response to pressure buildup. With non-ideal seals, brine may also leak through the seals into overlying/underlying formations. The quick-assessment method calculates these brine displacement contributions in response to an estimated average pressure buildup in the storage reservoir. The CO₂ storage capacity and the transient domain-averaged pressure buildup estimated through the quick-assessment method were compared with the “true” values obtained using detailed numerical simulations of CO₂ and brine transport in a two-dimensional radial system. The good agreement indicates that the proposed method can produce reasonable approximations for storage–formation–seal systems of various geometric and hydrogeological properties.     

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.     

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.     

Post-combustion CO2-capture from coal-fired power plants: Preliminary evaluation of an integrated chemical absorption process with piperazine-promoted potassium carbonate

The simulation tool ASPEN Plus^® is used to model the full CO₂-capture process for chemical absorption of CO₂ by piperazine-promoted potassium carbonate (K₂CO₃/PZ) and the subsequent CO₂-compression train. Sensitivity analysis of lean loading, desorber pressure and CO₂-capture rate are performed for various solvent compositions to evaluate the optimal process parameters. EbsilonProfessional^® is used to model a 600 MW_el (gross) hard coal-fired power plant. Numerical equations for power losses due to steam extraction for solvent regeneration are derived from simulation runs. The results of the simulation campaigns are used to find the process parameters that show the lowest specific power loss. Subsequently, absorber and desorber columns are dimensioned to evaluate investment costs for these main components of the CO₂-capture process. Regeneration heat duty, net efficiency losses and column investment costs are then compared to the reference case of CO₂-capture by monoethanolamine (MEA).CO₂-capture by piperazine-promoted potassium carbonate with subsequent CO₂-compression to 110 bar shows energetic advantages over the reference process which uses MEA. Additionally, investment costs for the main components in the CO₂-capture process (absorber and desorber columns) are lower due to the enhanced reaction kinetics of the investigated K₂CO₃/PZ solvent which leads to smaller component sizes.     

Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.