Derivation of correlations to evaluate the impact of retrofitted post-combustion CO2 capture processes on steam power plant performance

When integrating a post-combustion CO₂ capture process and CO₂ compression into a steam power plant, the three interface quantities heat, electricity and cooling duty must be satisfied by the power plant, leading to a loss in net efficiency. The heat duty shows to be the largest contributor to the overall net efficiency penalty of the power plant. Additional energy penalty results from the cooling and electric power duty of the capture and compression units.In this work, the dependency of the energy penalty on the quantity and quality of the heat duty is analyzed and quantified for a state-of-the-art hard coal fired power plant. Furthermore, the energy penalty attributed to the additional cooling and power duty is quantified. As a result correlations are provided which enable to predict the impact of the heat, cooling and electricity duty of post-combustion CO₂ capture processes on the net output of a steam power plant in a holistic approach.     

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.     

Designing a supercritical steam cycle to integrate the energy requirements of CO2 amine scrubbing

Absorption by chemical solvents combined with CO₂ long-term storage appears to offer interesting and commercial applicable CO₂ capture technology. However one of the main disadvantages is related to the large quantities of heat required to regenerate the amine solvent that means an important power plant efficiency penalty. Different studies have analyzed alternatives to reduce the heat duty on the reboiler and the thermal integration requirements on existing power cycles. In these studies integration principles have been well set up, but there is a lack of information about how to achieve an integrated design and the thermal balances of the modified cycle flowsheet. This paper proposes and provides details about a set of modifications of a supercritical steam cycle to overcome the energy requirements through energetic integration with the aim of reducing the efficiency and power output penalty associated with CO₂ capture process. Modifications include a new designed low-pressure heater flowsheet to take advantage of the CO₂ compression cooling for postcombustion systems and integration of amine reboiler into a steam cycle. It has been carried out several simulations in order to obtain power plant performance depending on sorbent regeneration requirements.     

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.     

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.     

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 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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Corrosion and polarization behavior of carbon steel in MEA-based CO2 capture process

This work reveals levels of corrosion rate and polarization behavior of carbon steel immersed in aqueous solutions of monoethanolamine (MEA) used in the absorption-based carbon dioxide (CO₂) capture process for greenhouse gas reduction from industrial flue gas streams. Such information was obtained from electrochemical-based corrosion experiments under a wide range of the CO₂ capture process conditions. The corrosion of carbon steel was evaluated in respect to process parameters including partial pressure of oxygen (O₂), CO₂ loading in solution, solution velocity, solution temperature, MEA concentration and metal surface condition. Results show that the aqueous MEA solution containing CO₂ provides a favorable condition for the corrosion of carbon steel to proceed. Corrosion rate is increased by all tested process parameters. These parametric effects were explained by the electrochemical kinetic data obtained from polarization curves and by the thermodynamic data obtained from Pourbaix diagram.     

Viscosities, thermal conductivities and diffusion coefficients of CO2 mixtures: Review of experimental data and theoretical models

Accurate experimental data on the thermo-physical properties of CO₂-mixtures are pre-requisites for development of more accurate models and hence, more precise design of CO₂ capture and storage (CCS) processes. A literature survey was conducted on both the available experimental data and the theoretical models associated with the transport properties of CO₂-mixtures within the operation windows of CCS. Gaps were identified between the available knowledge and requirements of the system design and operation. For the experimental gas-phase measurements, there are no available data about any transport properties of CO₂/H₂S, CO₂/COS and CO₂/NH₃; and except for CO₂/H₂O(/NaCl) and CO₂/amine/H₂O mixtures, there are no available measurements regarding the transport properties of any liquid-phase mixtures. In the prediction of gas-phase viscosities using Chapman–Enskog theory, deviations are typically <2% at atmospheric pressure and moderate temperatures. The deviations increase with increasing temperatures and pressures. Using both the Rigorous Kinetic Theory (RKT) and empirical models in the prediction of gas-phase thermal conductivities, typical deviations are 2.2–9%. Comparison of popular empirical models for estimation of gas-phase diffusion coefficients with newer experimental data for CO₂/H₂O shows deviations of up to 20%. For many mixtures relevant for CCS, the diffusion coefficient models based on the RKT show predictions within the experimental uncertainty. Typical reported deviations of the CO₂/H₂O system using empirical models are below 3% for the viscosity and the thermal conductivity and between 5 and 20% for the diffusion coefficients. The research community knows little about the effect of other impurities in liquid CO₂ than water, and this is an important area to focus in future work.     

Embodied energy and CO2 in UK dimension stone

A process based life cycle assessment of dimension stone production in the UK has been carried out according to PAS 2050. From a survey of eight production operations, on a cradle-to-site basis for UK destinations the carbon footprint of sandstone is 77 kgCO₂e/tonne, that of granite is 107 kgCO₂e/tonne and that of slate is 251 kgCO₂e/tonne. These values are considerably higher for stone imported from abroad due to the impact of transport. Reducing the reliance on imported stone will contribute to emissions reduction targets as well as furthering the goals of sustainable development.     

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.     

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.     

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.