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 modelling and analysis of post-combustion CO2 chemical absorption process for coal-fired power plants

Post-combustion capture by chemical absorption using MEA solvent remains the only commercial technology for large scale CO₂ capture for coal-fired power plants. This paper presents a study of the dynamic responses of a post-combustion CO₂ capture plant by modelling and simulation. Such a plant consists mainly of the absorber (where CO₂ is chemically absorbed) and the regenerator (where the chemical solvent is regenerated). Model development and validation are described followed by dynamic analysis of the absorber and regenerator columns linked together with recycle. The gPROMS (Process Systems Enterprise Ltd.) advanced process modelling environment has been used to implement the proposed work. The study gives insights into the operation of the absorber-regenerator combination with possible disturbances arising from integrated operation with a power generation plant. It is shown that the performance of the absorber is more sensitive to the molar L/G ratio than the actual flow rates of the liquid solvent and flue gas. In addition, the importance of appropriate water balance in the absorber column is shown. A step change of the reboiler duty indicates a slow response. A case involving the combination of two fundamental CO₂ capture technologies (the partial oxyfuel mode in the furnace and the post-combustion solvent scrubbing) is studied. The flue gas composition was altered to mimic that observed with the combination. There was an initial sharp decrease in CO₂ absorption level which may not be observed in steady-state simulations.     

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.     

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.     

Techno-economic optimization of IGCC integrated with utility system for CO2 emissions reduction—Maximum power production in IGCC

Environmental legislation, with its increasing pressure on the energy sector to control greenhouse gases, is a driving force to reduce CO₂ emissions. In this paper, pre-combustion CO₂ capture through integration of a site utility system with an integrated gasification combined cycle (IGCC) is investigated as an option to provide a compressed CO₂-rich stream from a process site for sequestration. This work presents a two-step procedure for integration and optimization of a site utility system with an IGCC plant: (i) screening and optimization of IGCC plant performance parameters; (ii) integration and optimization of the utility system of the site with the IGCC plant. In the first step, an optimization approach applies the results of screening studies based on rigorous simulation of the IGCC. Having fixed the inlet fuel flow rate, the IGCC design parameters (including oxygen consumption, diluent flow rate and turbine exit pressure) are optimized for maximum power generation. Energy flows between the IGCC and CO₂ compression train are considered. In the second step, the economic and operating performance of the utility system integrated with the IGCC plant are modeled and optimized for minimum operating cost to find the most appropriate level of integration. In a case study illustrating the approach, 94% of the fuel is gasified; additional power generation offsets the operating costs of pre-combustion CO₂ capture.     

A rate equation for Ca(OH)2 and CO2 reaction in a spouted bed reactor at low gas concentrations

In the present study, the carbonation reaction of hydrated lime in semi-dry condition is investigated experimentally in a laboratory-scale spouted bed reactor. Results show that for operating conditions where the concentration of CO₂ is low, the capture efficiency is raised by increasing the inlet CO₂ concentration. Additionally, because of the inconsistency between the experimental reaction rate and the calculated values based on the previous proposed equations, a new rate equation is introduced that considers the dependency of CO₂ concentration too. To validate the proposed equation, its predictions were compared with another set of experimental data.     

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.     

Poly(ethylene terephthalate) nanofibers prepared by CO2 laser supersonic drawing

Poly(ethylene terephthalate) (PET) nanofibers were prepared by irradiating a PET fiber with radiation from a carbon dioxide (CO₂) laser while drawing it at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through the fiber injection orifice. The flow velocity from the orifice was estimated by computer simulation; the fastest flow velocity was calculated to be 401 m s⁻¹ at a chamber pressure of 6 kPa. A nanofiber obtained using a laser power of 8 W and a chamber pressure of 6 kPa had an average diameter of 193 nm and a draw ratio of about 900,000. This technique is a novel method for producing nanofibers.     

Simultaneous optimization of CO2 emissions reduction strategies for effective carbon control in the process industries

Concerns about global warming have led governments to regulate CO₂ emissions, including through emissions caps, trading and penalties, thus creating economic incentives to reduce CO₂ emissions. This paper presents a mathematical model based on a MINLP formulation to address the problem of CO₂ emissions from large-scale sites in the process industries. The proposed approach considers the interactions between process units, associated heat exchanger networks and the site utility system. The CO₂ emissions reduction strategies considered include retrofit of heat exchanger networks (HENs), operational optimization of the utility system and fuel switching. The mathematical model captures interactions between the HEN and the utility system; the optimization explores these interactions systematically within a superstructure of CO₂ reduction options. The optimization objective is to determine suitable CO₂-mitigation options for a given emissions reduction target and available capital for investment, taking carbon trading issues into account. The proposed approach is applied to a published industrial case study; the results demonstrate the applicability of the approach to finding cost-effective solutions for CO₂ emissions reduction. Results show that the best solution CO₂ emissions reduction is affected by carbon trading. Therefore, opportunities to sell CO₂ allowances, if practically achievable, play an important role in the process economics.     

Techno-economic evaluation of advanced IGCC lignite coal fuelled power plants with CO2 capture

The techno-economic evaluation of four novel integrated gasification combined cycle (IGCC) power plants fuelled with low rank lignite coal with CO₂ capture facility has been investigated using ECLIPSE process simulator. The performance of the proposed plants was compared with two conventional IGCC plants with and without CO₂ capture. The proposed plants include an advanced CO₂ capturing process based on the Absorption Enhanced Reforming (AER) reaction and the regeneration of sorbent materials avoiding the need for sulphur removal component, shift reactor and/or a high temperature gas cleaning process. The results show that the proposed CO₂ capture plants efficiencies were 18.5–21% higher than the conventional IGCC CO₂ capture plant. For the proposed plants, the CO₂ capture efficiencies were found to be within 95.8–97%. The CO₂ capture efficiency for the conventional IGCC plant was 87.7%. The specific investment costs for the proposed plants were between 1207 and 1479 €/kW_e and 1620 €/kW_e and 1134 €/kW_e for the conventional plants with and without CO₂ capture respectively. Overall the proposed IGCC plants are cleaner, more efficient and produce electricity at cheaper price than the conventional IGCC process.     

Effect of solvent (CO2/ethanol/H2O) on the fractionated enhanced solvent extraction of anthocyanins from elderberry pomace

The management of agro-industrial residues is an important issue for environmental reasons and the reuse of byproducts represents a good alternative, especially if it is conjugated with green technologies and the production of valuable products. Portuguese elderberry pomace is rich in anthocyanins with therapeutic properties that confer to this byproduct potential to be applied in the food and pharmaceutical industries. Fractionated high pressure extractions from elderberry pomace were performed using supercritical CO₂ extraction, followed by enhanced solvent extraction (ESE) with diverse CO₂/ethanol/H₂O solvent mixtures (0-90%, 0.5-100%, 0-95%, v/v/v), at 313 K and 21 MPa, in order to obtain anthocyanin-rich fractions. The ESE solvent mixtures had a substantial effect on extracts yield and composition. The maximum extraction yield (24.2%), total phenolic compounds (15.8% gallic acid equivalents), total flavonoids (8.9% epicatechin equivalents), total anthocyanins (15.0% cyanidin-3-glucoside equivalents) and antioxidant activity (IC₅₀ of 21 μg) achieved highlight the great potential of elderberry pomace for valuable applications.     

Accelerated degradation method for cement under CO2-rich environment: The LIFTCO2 procedure (leaching induced by forced transport in CO2 fluids)

For emerging applications such as long-term CO₂ storage, establishing and maintaining well integrity during the life of the well pose significant challenges. Particularly, well cement will need to be durable under corrosive environments, such as exposure to CO₂-rich fluids, over a long period of time from 25 years to 100-1000 years. To model long-term cement durability in such severe environments, accelerated degradation methods must be considered and developed. This study presents experimental equipment and a procedure showing that it is possible to accelerate Portland cement degradation in the presence of CO₂ fluids by applying a potential gradient through a set cement sample in a CO₂ environment (the LIFTCO₂ procedure). The degradation pattern consists of a series of successive fronts penetrating the cement sample: a dissolution front, a carbonation front, and a gel layer. Such degradation is accelerated when increasing the potential gradient, the temperature, and the CO₂ concentration in the electrolyte.     

Intrinsic char reactivity of plastic waste (PET) during CO2 gasification

Char reactivity has a strong influence on the gasification process, since char gasification is the slowest step in the process. A sample of waste PET was devolatilised in a vertical quartz reactor and the resulting char was partially gasified under a CO₂ atmosphere at 925 °C in order to obtain samples with different degrees of conversion. The reactivity of the char in CO₂ was determined by isothermal thermogravimetric analysis at different temperatures in a kinetically controlled regime and its reactive behaviour was evaluated by means of the random pore model (RPM). The texture of the char was characterised by means of N₂ and CO₂ adsorption isotherms. The results did not reveal any variation in char reactivity during conversion, whereas the micropore surface area was affected during the gasification process. It was found that the intrinsic reaction rate of the char can be satisfactorily calculated by normalizing the reaction rate by the narrow micropore surface area calculated from the CO₂ adsorption isotherms. It can be concluded therefore that the surface area available for the gasification process is the area corresponding to the narrow microporosity.     

Vesicle formation of polystyrene-block-poly (ethylene oxide) block copolymers induced by supercritical CO2 treatment

A novel route for a preparation of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer vesicles induced by supercritical carbon dioxide (scCO₂) is demonstrated. When PS-b-PEO block copolymer solutions in tetrahydrofuran (THF) are treated with scCO₂ at 70 °C for different times, PS-b-PEO copolymers first assemble into aggregated spheres; then aggregated spheres change into large compound micelles and finally evolve into vesicles. The possible formation mechanism of the vesicles is discussed.     

Amine modified mesocellular siliceous foam (MCF) as a sorbent for CO2

Adsorption is considered a promising method for carbon capture. CO₂ adsorbents take a variety of forms - but one approach is to fill mesoporous substrates with a polymeric CO₂ selective sorbent. SBA-15 and mesocellular siliceous foam (MCF) are high pore volume, high surface area ordered mesoporous materials for which modification with amine should result in high capacity, highly selective adsorbents. SBA-15 and MCF were separately loaded with approximately one pore volume equivalent of linear polyethyleneimine (PEI) (M_w = 2500) or branched PEI (M_n = 1200). CO₂ adsorption/desorption isotherms under dry CO₂ were obtained at 75, 105 and 115 °C. The CO₂ adsorption/desorption kinetics were improved with temperature, though the CO₂ capacities generally decreased. The adsorption capacity for MCF loaded with branched PEI at 105 and 115 °C were 151 and 133 mg/g adsorbent, respectively (in 50% CO₂/Ar, 20 min adsorption time). These are significantly higher than the adsorption capacity observed for SBA-15 loaded with branched PEI under same conditions, which were 107 and 83 mg/g adsorbent, respectively. Thus the results indicate that, on a unit mass basis, amine modified MCF's are potentially better adsorbents than amine modified SBA-15 for CO₂ capture at modestly elevated temperature in a vacuum swing adsorption process.     

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.     

The calcium looping cycle for CO2 capture from power generation, cement manufacture and hydrogen production

Calcium looping is a CO₂ capture scheme using solid CaO-based sorbents to remove CO₂ from flue gases, e.g., from a power plant, producing a concentrated stream of CO₂ (∼95%) suitable for storage. The scheme exploits the reversible gas-solid reaction between CO₂ and CaO(s) to form CaCO₃(s). Calcium looping has a number of advantages compared to closer-to-market capture schemes, including: the use of circulating fluidised bed reactors—a mature technology at large scale; sorbent derived from cheap, abundant and environmentally benign limestone and dolomite precursors; and the relatively small efficiency penalty that it imposes on the power/industrial process (i.e., estimated at 6-8 percentage points, compared to 9.5-12.5 from amine-based post-combustion capture). A further advantage is the synergy with cement manufacture, which potentially allows for decarbonisation of both cement manufacture and power production. In addition, a number of advanced applications offer the potential for significant cost reductions in the production of hydrogen from fossil fuels coupled with CO₂ capture. The range of applications of calcium looping are discussed here, including the progress made towards demonstrating this technology as a viable post-combustion capture technology using small-pilot scale rigs, and the early progress towards a 2 MW scale demonstrator.