Dynamic modelling of CO2 absorption for post combustion capture in coal-fired power plants

Power generation from fossil fuel-fired power plants is the largest single source of CO₂ emissions. Post combustion capture via chemical absorption is viewed as the most mature CO₂ capture technique. This paper presents a study of the post combustion CO₂ capture with monoethanolamine (MEA) based on dynamic modelling of the process. The aims of the project were to compare two different approaches (the equilibrium-based approach versus the rate-based approach) in modelling the absorber dynamically and to understand the dynamic behaviour of the absorber during part load operation and with disturbances from the stripper. A powerful modelling and simulation tool gPROMS was chosen to implement the proposed work. The study indicates that the rate-based model gives a better prediction of the chemical absorption process than the equilibrium-based model. The dynamic simulation of the absorber indicates normal absorber column operation could be maintained during part load operation by maintaining the ratio of the flow rates of the lean solvent and flue gas to the absorber. Disturbances in the CO₂ loading of the lean solvent to the absorber significantly affect absorber performance. Further work will extend the dynamic modelling to the stripper for whole plant analysis.     

Dynamic modeling of CO2 absorption from coal-fired power plants into an aqueous monoethanolamine solution

Among carbon capture and storage (CCS), the post-combustion capture of carbon dioxide (CO₂) by means of chemical absorption is actually the most developed process. Steady state process simulation turned out as a powerful tool for the design of such CO₂ scrubbers. Besides steady state modeling, transient process simulations deliver valuable information on the dynamic behavior of the system. Dynamic interactions of the power plant with the CO₂ separation plant can be described by such models. Within this work a dynamic process simulation model of the absorption unit of a CO₂ separation plant was developed. For describing the chemical absorption of CO₂ into an aqueous monoethanolamine solution a rate based approach was used. All models were developed within the Aspen Custom Modeler^® simulation environment. Thermo physical properties as well as transport properties were taken from the electrolyte non-random-two-liquid model provided by the Aspen Properties^® database. Within this work two simulation cases are presented. In a first simulation the inlet temperature of the flue gas and the lean solvent into the absorber column was changed. The results were validated by using experimental data from the CO₂SEPPL test rig located at the Dürnrohr power station. In a second simulation the flue gas flow to the separation plant was increased. Due to the unavailability of experimental data a validation of the results from the second simulation could not be achieved.     

Partial O2-fired coal power plant with post-combustion CO2 capture: A retrofitting option for CO2 capture ready plants

In the work presented in this paper, an alternative process concept that can be applied as retrofitting option in coal-fired power plants for CO₂ capture is examined. The proposed concept is based on the combination of two fundamental CO₂ capture technologies, the partial oxyfuel mode in the furnace and the post-combustion solvent scrubbing. A 330 MW_el Greek lignite-fired power plant and a typical 600 MW_el hard coal plant have been examined for the process simulations. In a retrofit application of the ECO-Scrub technology, the existing power plant modifications are dominated by techno-economic restrictions regarding the boiler and the steam turbine islands. Heat integration from processes (air separation, CO₂ compression and purification and the flue gas treatment) can result in reduced energy and efficiency penalties. In the context of this work, heat integration options are illustrated and main results from thermodynamic simulations dealing with the most important features of the power plant with CO₂ capture are presented for both reference and retrofit case, providing a comparative view on the power plant net efficiency and energy consumptions for CO₂ capture. The operational characteristics as well as the main figures and diagrams of the plant’s heat balances are included.     

Dynamic modeling and validation of absorber and desorber columns for post-combustion CO2 capture

The paper evaluates, by modeling and simulation, carbon dioxide capture in aqueous solution of mono-ethanolamine (MEA) in packed absorption columns to be used in power sector for reducing greenhouse gas emissions. The mathematical model of carbon dioxide absorption and rich amine regeneration process includes transfer processes: mass and heat to study the coupled effect of temperature and concentration on the rate of absorption. The reaction kinetics and the vapor-liquid equilibrium (VLE) are other important parts of the model. The present dynamic mathematical model can be used to analyze the absorption rate, to understand the micro level interaction of various processes taking place inside the absorption and desorption column, and to improve the overall design of the system.The aim of the project was to validate the absorber and desorber models, as well as to understand the dynamic behavior of the whole capture-regeneration steps.     

Modelling reactive absorption of CO2 in packed columns for post-combustion carbon capture applications

A rate-based process model for the reactive absorption of carbon dioxide (CO₂) from a gas mixture into an aqueous monoethanolamine (MEA) solution in a packed column is developed. The model is based on the fast second-order kinetics for the CO₂-MEA reactions and takes into account the mass transfer resistances. The heat effects associated with the absorption and chemical reaction are included through energy balances in the gas and liquid phases. Appropriate correlations for the key thermodynamic and transport properties and for the gas-liquid mass transfer are incorporated into the model to ensure reliable predictions. The model predictions are validated by simulating a series of experiments conducted in pilot and industrial scale absorption columns with random and structured packings reported in the literature. Comparisons between the simulation results and the experimental data reveal good quality predictions of the gas phase CO₂ and MEA concentrations and the liquid temperature along the column height. The sensitivity studies reveal that the correlations for the gas- and liquid-film mass transfer coefficients given by Onda et al. (1968) provide better predictions than the penetration theory of Higbie (1935) and the correlation of Bravo et al. (1985).     

Optimization of post-combustion CO2 process using DEA-MDEA mixtures

This paper presents optimal operating conditions for the post-combustion CO₂ capture process utilizing aqueous amine solutions obtained using a process simulator (HYSYS). Three alkanolamine solutions (Methyldiethanolamine MDEA, DiEthanolAmine DEA and MDEA-DEA mixture) are considered to study the performance of the capture process.The design problem addressed in this paper requires specifying the optimal operating conditions (inlet and outlet temperature of the lean solution stream on the absorber, CO₂ loading, amine composition and flow rates, among others) to achieve the given CO₂ emission targets at a minimum total annual cost. A detailed objective function including total operating costs and investment is considered.The influence of the variation of CO₂ reduction targets and the mixing proportion of amines on the total annual cost is analyzed in detail. Numerical results are presented and discussed using different case studies.The results demonstrate that process simulators can be used as a powerful tool not only to simulate but also to optimize the most important design parameters of the post-combustion CO₂ capture process.     

Impact of liquid absorption process development on the costs of post-combustion capture in Australian coal-fired power stations

Australian power generators produce approximately 170 TWh per annum of electricity using black and brown coals that accounts for 170 Mtonne of CO₂ emissions per annum or over 40% of anthropogenic CO₂ emissions in Australia. This paper describes the results of a techno-economic evaluation of liquid absorption based post-combustion capture (PCC) processes for both existing and new pulverised coal-fired power stations in Australia. The overall process designs incorporate both the case with continuous capture and the case with the flexibility to switch a CO₂ capture plant on or off depending upon the demand and market price for electricity, and addresses the impact of the presently limited emission controls on the process cost. The techno-economic evaluation includes both air and water cooled power and CO₂ capture plants, resulting in cost of power generation for the situations without and with PCC. Whilst existing power plants in Australia are all water cooled sub-critical designs, the new power plants are deemed to range from supercritical single reheat to ultra-supercritical double reheat designs, with a preference for air-cooling. The process evaluation also includes a detailed sensitivity analysis of the thermodynamic properties of liquid absorbent for CO₂ on the overall costs. The results show that for a meaningful decrease in the efficiency and cost penalties associated with the post combustion CO₂ capture, a novel liquid sorbent will need to have heat of absorption/desorption, sensible heat and heat of vaporisation around 50% less in comparison with 30% (w/w) aqueous MEA solvent. It also shows that the impact of the capital costs of PCC processes is quite large on the added cost of generation. The results can be used to prioritise PCC research in an Australian context.     

Preliminary analysis of process flow sheet modifications for energy efficient CO2 capture from flue gases using chemical absorption

The energy penalty associated with solvent based capture of CO₂ from power station flue gases can be reduced by incorporating process flow sheet modifications into the standard process. A review of modifications suggested in the open and patent literature identified several options, primarily intended for use in the gas processing industry. It was not immediately clear whether these options would have the same benefits when applied to CO₂ capture from near atmospheric pressure combustion flue gases. Process flow sheet modifications, including split flow, rich split, vapour recompression, and inter-stage cooling, were therefore modelled using a commercial rate-based simulation package. The models were completed for a Queensland (Australia) based pilot plant running on 30% MEA as the solvent. The preliminary modelling results showed considerable benefits in reducing the energy penalty of capturing CO₂ from combustion flue gases. Further work will focus on optimising and validating the most relevant process flow sheet modifications in a pilot plant.     

Post-combustion CO2 capture with chemical absorption: A state-of-the-art review

Global concentration of CO₂ in the atmosphere is increasing rapidly. CO₂ emissions have an impact on global climate change. Effective CO₂ emission abatement strategies such as Carbon Capture and Storage (CCS) are required to combat this trend. There are three major approaches for CCS: post-combustion capture, pre-combustion capture and oxyfuel process. Post-combustion capture offers some advantages as existing combustion technologies can still be used without radical changes on them. This makes post-combustion capture easier to implement as a retrofit option (to existing power plants) compared to the other two approaches. Therefore, post-combustion capture is probably the first technology that will be deployed. This paper aims to provide a state-of-the-art assessment of the research work carried out so far in post-combustion capture with chemical absorption. The technology will be introduced first, followed by required preparation of flue gas from power plants to use this technology. The important research programmes worldwide and the experimental studies based on pilot plants will be reviewed. This is followed by an overview of various studies based on modelling and simulation. Then the focus is turned to review development of different solvents and process intensification. Based on these, we try to predict challenges and potential new developments from different aspects such as new solvents, pilot plants, process heat integration (to improve efficiency), modelling and simulation, process intensification and government policy impact.     

A NGCC power plant with a CO2 post-combustion capture option. Optimal economics for different generation/capture goals

Fossil fuel power plants are one of the major sources of electricity generation, although invariably release greenhouse gases. Due to international treaties and countries regulations, CO₂ emissions reduction is increasingly becoming key in the generators’ economics. NGCC power plants constitute a widely used generation technology, from which CO₂ capture through a post-combustion and MEA absorption option constitutes a technological challenge due to the low concentration of pollutants in the flue gas and the high energy requirements of the sequestration process.     

On the integration of CO2 capture with coal-fired power plants: A methodology to assess and optimise solvent-based post-combustion capture systems

Amine and other liquid solvent CO₂ capture systems capture have historically been developed in the oil and gas industry with a different emphasis to that expected for fossil fuel power generation with post-combustion capture. These types of units are now being adapted for combustion flue gas scrubbing for which they need to be designed to operate at lower CO₂ removal rates - around 85-90% and to be integrated with CO₂ compression systems. They also need to be operated as part of a complete power plant with the overall objective of turning fuel into low-carbon electricity.The performance optimisation approach for solvents being considered for post-combustion capture in power generation therefore needs to be updated to take into account integration with the power cycle and the compression train. The most appropriate metric for solvent assessment is the overall penalty on electricity output, rather than simply the thermal energy of regeneration of the solvent used.Methodologies to evaluate solvent performance that have been reported in the literature are first reviewed. The results of the model of a steam power cycle integrated with the compression system focusing on key parameters of the post-combustion capture plant - solvent energy of regeneration, solvent regeneration temperature and desorber pressure - are then presented. The model includes a rigorous thermodynamic integration of the heat available in the capture and compression units into the power cycle for a range of different solvents, and shows that the electricity output penalty of steam extraction has a strong dependence on solvent thermal stability and the temperature available for heat recovery. A method is provided for assessing the overall electricity output penalty (EOP), expressed as total kWh of lost output per tonne of CO₂ captured including ancillary power and compression, for likely combinations of these three key post-combustion process parameters. This correlation provides a more representative method for comparing post-combustion capture technology options than the use of single parameters such as solvent heat of regeneration.     

Post-combustion CO2 capture process: Equilibrium stage mathematical model of the chemical absorption of CO2 into monoethanolamine (MEA) aqueous solution

This paper deals with the modeling and optimization of the chemical absorption process to CO₂ removal using monoethanolamine (MEA) aqueous solution. Precisely, an optimization mathematical model is proposed to determine the best operating conditions of the CO₂ post-combustion process in order to maximize the CO₂ removal efficiency. Certainly, the following two objective functions are considered for maximization: (a) ratio between the total absorbed CO₂ and the total heating and cooling utilities and (b) ratio between total absorbed CO₂ and the total amine flow-rate.Temperature, composition and flow-rate profiles of the aqueous solution and gas streams along the absorber and regenerator as well as the reboiler and condenser duties are considered as optimization variables. The number of trays or height equivalent to a theoretical plate (HETP) on the absorber and regenerator columns as well as the CO₂ composition in flue gas are treated as model parameters. Correlations used to compute physical-chemical properties of the aqueous amine solution are taken from different specialized literature and are valid for a wide range of operating conditions. For the modeling, both columns (absorber and regenerator) are divided into a number of segments assuming that liquid and gas phases are well mixed.GAMS (General Algebraic Modeling System) and CONOPT are used, respectively, to implement and to solve the resulting mathematical model.The robustness and computational performance of the proposed model and a detailed discussion of the optimization results will be presented through different case studies. Finally, the proposed model cannot only be used as optimizer but also as a simulator by fixing the degree of freedom of the equation system.     

Thermodynamic performance of O2/CO2 gas turbine cycle with chemical recuperation by CO2-reforming of methane

This paper proposes a novel power cycle system composed of chemical recuperative cycle with CO₂–NG (natural gas) reforming and an ammonia absorption refrigeration cycle. In which, the heat is recovered from the turbine exhaust to drive CO₂–NG reformer firstly, and then lower temperature heat from the turbine exhaust is provided with the ammonia absorption refrigeration system to generate chilled media, which is used to cool the turbine inlet gas except export. In this paper, a detailed thermodynamic analysis is carried out to reveal the performance of the proposed cycle and the influence of key parameters on performance is discussed. Based on 1 kg s⁻¹ of methane feedstock and the turbine inlet temperature of 1573 K, the simulation results shown that the optimized net power generation efficiency of the cycle rises up to 49.6% on the low-heating value and the exergy efficiency 47.9%, the new cycle system reached the net electric-power production 24.799 MW, the export chilled load 0.609 MW and 2.743 kg s⁻¹ liquid CO₂ was captured, achieved the goal of CO₂ and NO_x zero-emission.     

An economic feasibility study of O2/CO2 recycle combustion technology based on existing coal-fired power plants in China

In order to reduce the CO₂ emission from the coal-fired power plants, O₂/CO₂ recycle combustion (Oxy-combustion) technique has been proposed through combining a conventional combustion process with a cryogenic air separation process. The technique is capable of enriching CO₂ concentration and then allowing CO₂ sequestration in an efficient and energy-saving way. Taking into account the CO₂ taxation and CO₂ sale, the paper evaluates the economic feasibility of Oxy-combustion plants retrofitted from two typical existing conventional coal-fired power plants (with capacities of 2 × 300 MW and 2 × 600 MW, respectively) with Chinese data. The cost of electricity (COE) and the CO₂ avoidance cost (CAC) are also considered in the evaluation. The COE of the retrofitted Oxy-combustion plant is nearly the same as that of the corresponding conventional plant if the unit price of CO₂ sale reaches 17-22 $/t (different cases). The CAC of the retrofitted 2 × 300 MW Oxy-combustion plant is 1-3 $/t bigger than that of the retrofitted 2 × 600 MW Oxy-combustion plant. Supercritical plants are more economical and appropriate for Oxy-combustion retrofit. The result indicates that Oxy-combustion technique is not only feasible for CO₂ emission control based on existing power plants but is also cost-effective.     

CO2 capture using oxygen enhanced combustion strategies for natural gas power plants

This paper describes a series of experiments conducted with natural gas in air and in mixtures of oxygen and recycled flue gas, termed O₂/CO₂ recycle combustion. The objective is to enrich the flue gas with CO₂ to facilitate its capture and sequestration. Detailed measurements of gas composition, flame temperature and heat flux profiles were taken inside CANMET's 0.3 MWth down-fired vertical combustor fitted with a proprietary pilot scale burner. Flue gas composition was continuously monitored. The effects of burner operation, including swirling of secondary stream and air staging, on flame characteristics and NO_x emissions were also studied. The results of this work indicate that oxy-gas combustion techniques based on O₂/CO₂ combustion with flue gas recycle offer excellent potential for retrofit to conventional boilers for CO₂ emission abatement. Other benefits of the technology include considerable reduction and even elimination of NO_x emissions, improved plant efficiency due to lower gas volume and better operational flexibility.     

Economical assessment of competitive enhanced limestones for CO2 capture cycles in power plants

CO₂ capture systems based on the carbonation/calcination loop have gained rapid interest due to promising carbonator CO₂ capture efficiency, low sorbent cost and no flue gases treatment is required before entering the system. These features together result in a competitively low cost CO₂ capture system. Among the key variables that influence the performance of these systems and their integration with power plants, the carbonation conversion of the sorbent and the heat requirement at calciner are the most relevant. Both variables are mainly influenced by CaO/CO₂ ratio and make-up flow of solids. New sorbents are under development to reduce the decay of their carbonation conversion with cycles. The aim of this study is to assess the competitiveness of new limestones with enhanced sorption behaviour applied to carbonation/calcination cycle integrated with a power plant, compared to raw limestone. The existence of an upper limit for the maximum average capture capacity of CaO has been considered. Above this limit, improving sorbent capture capacity does not lead to the corresponding increase in capture efficiency and, thus, reduction of CO₂ avoided cost is not observed. Simulations calculate the maximum price for enhanced sorbents to achieve a reduction in CO₂ removal cost under different process conditions (solid circulation and make-up flow). The present study may be used as an assessment tool of new sorbents to understand what prices would be competitive compare with raw limestone in the CO₂ looping capture systems.     

Techno-economic evaluation of a PVAm CO2-selective membrane in an IGCC power plant with CO2 capture

Published data for an operating power plant, the ELCOGAS 315 MWe Puertollano plant, has been used as a basis for the simulation of an integrated gasification combined cycle process with CO₂ capture. This incorporated a fixed site carrier polyvinylamine membrane to separate the CO₂ from a CO-shifted syngas stream. It appears that the modified process, using a sour shift catalyst prior to sulphur removal, could achieve greater than 85% CO₂ recovery at 95 vol% purity. The efficiency penalty for such a process would be approximately 10% points, including CO₂ compression. A modified plant with CO₂ capture and compression was calculated to cost €2320/kW, producing electricity at a cost of 7.6 € cents/kWh and a CO₂ avoidance cost of about €40/tonne CO₂.     

Simulation and thermodynamic analysis of chemical looping reforming and CO2 enhanced chemical looping reforming

The production of hydrogen from methane via two chemical looping reforming (CLR) processes was simulated and thermodynamically analysed, one process being the conventional CLR process, the other being a CO₂ sorption enhanced process. The aim of the work was to identify suitable operating conditions for obtaining an optimum hydrogen gas purity and yield, whilst operating auto-thermally, at atmospheric pressure and with no carbon formation. In both simulations, the reactors were simulated using the Gibbs minimisation technique. NiO was used as the oxygen storing species, whilst CaO was used as the CO₂ adsorbent.     

Initial evaluation of the impact of post-combustion capture of carbon dioxide on supercritical pulverised coal power plant part load performance

Pulverised coal-fired plants often play an important role in electricity grids as mid-merit plants that can operate flexibly in response to changes in supply and demand. As a consequence, these plants are required to operate over a wide output range. This paper presents an initial evaluation of some potential impacts of adding post-combustion CO₂ capture on the part load performance of pulverised coal-fired plants. Preliminary results for ideal cases analysed using a simple high-level model indicate that post-combustion CO₂ capture could increase the options available to power plant operators. In particular, solvent storage could allow higher effective plant load factors to be achieved to assist with capital recovery while still permitting flexible operation for grid support. A number of areas for more detailed analysis are identified.     

A systematic approach to assessing measurement uncertainty for CO2 emissions from coal-fired power plants - Missing contributions from the Theory of Sampling (TOS)

An augmented measurement uncertainty approach for CO₂ emissions from coal-fired power plants with a focus on the often forgotten contributions from sampling errors occurring over the entire fuel-to-emission pathway is presented. Current methods for CO₂ emission determination are evaluated in detail, from which a general matrix scheme is developed that includes all factors and stages needed for total CO₂ determination, which is applied to the monitoring plan of a representative medium-sized coal-fired power plant. In particular sampling involved significant potential errors, as identified and assessed by the Theory of Sampling (TOS), which also shows how these can be eliminated and/or minimised. Since coal-related CO₂ emission calculations not only require analytical results of the carbon content of coal itself but also of the by-products fly ash and bottom ash, sampling procedures of these three materials were also given full attention. A systematic error (bias) is present in the current sampling approach, which increases the present uncertainty estimate unnecessarily. For both primary sampling and analytical sample extraction steps, random variations, which hitherto only have been considered to a minor extent, have now also been fully quantified and included in the overall uncertainty. Elimination of all identified sampling errors lead to modified CO₂ determination procedures, which indicate that the actual CO₂ emission is approximately 20,000 t higher than the present estimate. Based on extensive empirical sampling experiments, a fully comprehensive uncertainty estimate procedure has been devised. Even though uncertainties increased (indeed one particular factor is substantially higher, the so-called “emission factor”), the revised CO₂ emission budget for the case plant complies with the official pre-determined uncertainty levels maxima in the EU guidelines.