CO2 capture from combined cycles integrated with Molten Carbonate Fuel Cells

In this paper Molten Carbonate Fuel Cells (MCFCs) are considered for their potential application in carbon dioxide separation when integrated into natural gas fired combined cycles. The MCFC performs on the anode side an electrochemical oxidation of natural gas by means of CO₃^2? ions which, as far as carbon capture is concerned, results in a twofold advantage: the cell removes CO₂ fed at the cathode to promote carbonate ion transport across the electrolyte and any dilution of the oxidized products is avoided.The MCFC can be “retrofitted” into a combined cycle, giving the opportunity to remove most of the CO₂ contained in the gas turbine exhaust gases before they enter the heat recovery steam generator (HRSG), and allowing to exploit the heat recovery steam cycle in an efficient “hybrid” fuel cell + steam turbine configuration. The carbon dioxide can be easily recovered from the cell anode exhaust after combustion with pure oxygen (supplied by an air separation unit) of the residual fuel, cooling of the combustion products in the HRSG and water separation. The resulting power cycle has the potential to keep the overall cycle electrical efficiency approximately unchanged with respect to the original combined cycle, while separating 80% of the CO₂ otherwise vented and limiting the size of the fuel cell, which contributes to about 17% of the total power output so that most of the power capacity relies on conventional low cost turbo-machinery. The calculated specific energy for CO₂ avoided is about 4 times lower than average values for conventional post-combustion capture technology. A sensitivity analysis shows that positive results hold also changing significantly a number of MCFC and plant design parameters.     

Design and off-design analyses of a pre-combustion CO2 capture process in a natural gas combined cycle power plant

In this study, a cycle designed for capturing the greenhouse gas CO₂ in a natural gas combined cycle power plant has been analyzed. The process is a pre-combustion CO₂ capture cycle utilizing reforming of natural gas and removal of the carbon in the fuel prior to combustion in the gas turbine. The power cycle consists of a H₂-fired gas turbine and a triple pressure steam cycle. Nitrogen is used as fuel diluent and steam is injected into the flame for additional NO_x control. The heat recovery steam generator includes pre-heating for the various process streams. The pre-combustion cycle consists of an air-blown auto-thermal reformer, water–gas shift reactors, an amine absorption system to separate out the CO₂, as well as a CO₂ compression block. Included in the thermodynamic analysis are design calculations, as well as steady-state off-design calculations. Even though the aim is to operate a plant, as the one in this study, at full load there is also a need to be able to operate at part load, meaning off-design analysis is important. A reference case which excludes the pre-combustion cycle and only consists of the power cycle without CO₂ capture was analyzed at both design and off-design conditions for comparison. A high degree of process integration is present in the cycle studied. This can be advantageous from an efficiency stand-point but the complexity of the plant increases. The part load calculations is one way of investigating how flexible the plant is to off-design conditions. In the analysis performed, part load behavior is rather good with efficiency reductions from base load operation comparable to the reference combined cycle plant.     

The modelling of a hybrid combined cycle with pressurised fluidised bed combustion and CO2 capture

This study investigates the possibility of capturing CO₂ from flue gas under pressurised conditions, which could prove to be beneficial in comparison to working under atmospheric conditions. Simulations of two hybrid combined cycles with pressurised fluidised bed combustion and CO₂ capture are presented. CO₂ is captured from pressurised flue gas by means of chemical absorption after the boiler but before expansion. The results show a CO₂ capture penalty of approximately 8 percentage points (including 90% CO₂ capture rate and compression to 110 bar), which makes the efficiency for the best performing cycle 43.9%. It is 5.2 percentage points higher than the most probable alternative, i.e. using a natural gas fired combined cycle and a pulverised coal fired condensing plant separately with the same fuel split ratio. The largest part of the penalty is associated with the lower mass flow of flue gas after CO₂ capture, which leads to a decrease in work output in the expander and potential for feed water heating. The penalty caused by the regeneration of absorbent is quite low, since the high pressure permits the use of potassium carbonate, which requires less regeneration heat than for example the more commonly proposed monoethanolamine. Although the efficiencies of the cycles look promising it will be important to perform a cost estimate to be able to make a fair comparison with other systems. Such a cost estimate has not been done in this study. A significant drawback of these hybrid cycles in that respect is the complex nature of the systems that will have a negative effect on the economy.     

Thermodynamic analysis on post-combustion CO2 capture of natural-gas-fired power plant

A chemical absorption, post-combustion CO₂ capture unit is simulated and an exergy analysis has been conducted, including irreversibility calculations for all process units. By pinpointing major irreversibilities, new proposals for efficient energy integrated chemical absorption process are suggested. Further, a natural-gas combined-cycle power plant with a CO₂ capture unit has been analyzed on an exergetic basis. By defining exergy balances and black-box models for plant units, investigation has been made to determine effect of each unit on the overall exergy efficiency. Simulation of the chemical absorption plant was done using UniSim Design software with Amines Property Package. For natural-gas combined-cycle design, GT PRO software (Thermoflow, Inc.) has been used. For exergy calculations, spreadsheets are created with Microsoft Excel by importing data from UniSim and GT PRO. Results show the exergy efficiency of 21.2% for the chemical absorption CO₂ capture unit and 67% for the CO₂ compression unit. The total exergy efficiency of CO₂ capture and compression unit is 31.6%.     

Life cycle assessment of natural gas combined cycle power plant with post-combustion carbon capture,transport and storage

Hybrid life cycle assessment has been used to assess the environmental impacts of natural gas combined cycle (NGCC) electricity generation with carbon dioxide capture and storage (CCS). The CCS chain modeled in this study consists of carbon dioxide (CO₂) capture from flue gas using monoethanolamine (MEA), pipeline transport and storage in a saline aquifer.Results show that the sequestration of 90% CO₂ from the flue gas results in avoiding 70% of CO₂ emissions to the atmosphere per kWh and reduces global warming potential (GWP) by 64%. Calculation of other environmental impacts shows the trade-offs: an increase of 43% in acidification, 35% in eutrophication, and 120–170% in various toxicity impacts. Given the assumptions employed in this analysis, emissions of MEA and formaldehyde during capture process and generation of reclaimer wastes contributes to various toxicity potentials and cause many-fold increase in the on-site direct freshwater ecotoxicity and terrestrial ecotoxicity impacts. NO_x from fuel combustion is still the dominant contributor to most direct impacts, other than toxicity potentials and GWP. It is found that the direct emission of MEA contribute little to human toxicity (HT < 1%), however it makes 16% of terrestrial ecotoxicity impact. Hazardous reclaimer waste causes significant freshwater and marine ecotoxicity impacts. Most increases in impact are due to increased fuel requirements or increased investments and operating inputs.The reductions in GWP range from 58% to 68% for the worst-case to best-case CCS system. Acidification, eutrophication and toxicity potentials show an even large range of variation in the sensitivity analysis. Decreases in energy use and solvent degradation will significantly reduce the impact in all categories.     

Life cycle modelling of fossil fuel power generation with post-combustion CO2 capture

Due to its compatibility with the current energy infrastructures and the potential to reduce CO₂ emissions significantly, CO₂ capture and geological storage is recognised as one of the main options in the portfolio of greenhouse gas mitigation technologies being developed worldwide. The CO₂ capture technologies offer a number of alternatives, which involve different energy consumption rates and subsequent environmental impacts. While the main objective of this technology is to minimise the atmospheric greenhouse gas emissions, it is also important to ensure that CO₂ capture and storage does not aggravate other environmental concerns. This requires a holistic and system-wide environmental assessment rather than focusing on the greenhouse gases only. Life Cycle Assessment meets this criteria as it not only tracks energy and non-energy-related greenhouse gas releases but also tracks various other environmental releases, such as solid wastes, toxic substances and common air pollutants, as well as the consumption of other resources, such as water, minerals and land use. This paper presents the principles of the CO₂ capture and storage LCA model developed at Imperial College and uses the pulverised coal post-combustion capture example to demonstrate the methodology in detail. At first, the LCA models developed for the coal combustion system and the chemical absorption CO₂ capture system are presented together with examples of relevant model applications. Next, the two models are applied to a plant with post-combustion CO₂ capture, in order to compare the life cycle environmental performance of systems with and without CO₂ capture. The LCA results for the alternative post-combustion CO₂ capture methods (including MEA, K⁺/PZ, and KS-1) have shown that, compared to plants without capture, the alternative CO₂ capture methods can achieve approximately 80% reduction in global warming potential without a significant increase in other life cycle impact categories. The results have also shown that, of all the solvent options modelled, KS-1 performed the best in most impact categories.     

Integration and evaluation of a power plant with a CaO-based CO2 capture system

This paper explores the integration and evaluation of a power plant with a CaO-based CO₂ capture system. There is a great amount of recoverable heat in the CaO-based CO₂ capture process. Five cases for the possible integration of a 600 MW power plant with CaO-based CO₂ capture process are considered in this paper. When the system is configured so that recovered heat is used to replace part of the boiler heat load (Case 2), modelling not only shows that this is the system recovering the most heat of 1008.8 MW but also results in the system with the lowest net power output of 446 MW and the second lowest of efficiency of 34.1%. It is indicated that system performance depends both on the amount of heat recovery and the type of heat utilization. When the system is configured so that a 400 MW power plant is built using the recovered heat (Case 4), modelling shows that this is the system with the most net power output of 846 MW, the highest efficiency of 36.8%, the lowest cost of electricity of 54.3 €/MWh and the lowest cost of CO₂ avoided of 28.9 €/tCO₂. This new built steam cycle will not affect the operation of the reference plant which vents its CO₂ to the atmosphere, highly reducing the connection between the CO₂ capture process and the reference plant which vents its CO₂ to the atmosphere. The average cost of electricity and the cost of CO₂ avoided of the five cases are about 58.9 €/kWh and 35.9 €/tCO₂, respectively.     

Multi-stage chemical looping combustion (CLC) for combined cycles with CO2 capture

This paper presents application of the chemical looping combustion (CLC) method in natural gas-fired combined cycles for power generation with CO₂ capture. A CLC combined cycle consisting of single CLC-reactor system, an air turbine, a CO₂-turbine and a steam cycle has been designated as the base-case cycle. The base-case cycle can achieve net plant efficiency of about 52% at an oxidation temperature of 1200 °C. In order to achieve a reasonable efficiency at lower oxidation temperatures, reheat is introduced into the air turbine by employing multi CLC-reactors. The results show that the single reheat CLC-combined cycle can achieve net plant efficiency of above 51% at oxidation temperature of 1000 °C and above 53% at the oxidation temperature of 1200 °C including CO₂ compression to 110 bar. The double reheat cycle results in marginal efficiency improvement as compared to the single reheat cycle. The CLC-cycles are also compared with a conventional combined cycle with and without post-combustion capture in amine solution. All the CLC-cycles show higher net plant efficiencies with close to 100% CO₂ capture as compared to a conventional combined cycle with post-combustion capture, which is very promising.     

Co-production of hydrogen and electricity with CO2 capture

Electricity and hydrogen can be used as energy carriers to reduce emissions of CO₂ from small and mobile energy users. One of the most promising technologies for the production of electricity and hydrogen with low CO₂ emissions is coal gasification with CO₂ capture and storage. Performance and cost data are presented for plants which produce electricity and hydrogen alone and plants which co-produce both of these energy carriers. The co-production plants include plants which produce a fixed ratio of hydrogen to electricity and plants which are able to vary the ratio while continuing to operate the gasification and CO₂ capture parts of the plant at full load. The paper also assesses the ability of these types of plants to satisfy the varying demands for hydrogen and electricity in future energy supply systems. The lowest cost option for the scenarios assessed in the paper is the use of flexible co-production plants with underground buffer storage of hydrogen.     

Calcium oxide for CO2 capture: Operational window and efficiency penalty in sorption-enhanced steam methane reforming

Calcium oxide (CaO) is a material that is being widely investigated in the context of CO₂ capture. One such application is as a CO₂ sorbent in the sorption-enhanced steam methane reforming processes (SERP). CO₂ is captured in an adsorption mode, where the conversion of CH₄ to H₂ is also enhanced, and released later in a separate desorption mode. This work presents an analysis of the relation between different process conditions and parameters during both adsorption and desorption modes. The interrelation between these conditions and the sorbent properties as well as the targeted carbon capture ratio is analysed. Conditions relevant for capturing 85% of carbon in the feed on CaO are determined and interlinked. A steam-to-carbon ratio of 4.2 has been determined to be relevant under 600 °C and 17 bar adsorption conditions. Similarly, process conditions relevant for regenerating the sorbent are determined and interlinked. For purge steam-to-CO₂ ratio of 1.8 at a desorption pressure of 1 bar, relevant desorption temperature has been calculated to be 820 °C. System simulations under these adsorption and desorption conditions resulted in a system efficiency of 50.8%. Effect of tuning process operating conditions on system efficiency as well as the efficiency penalty associated with the regeneration of the sorbent are investigated by process simulations using Aspen Plus^®. Possible system heat integration routes to reduce the efficiency penalty are proposed and the results of the process simulations are presented.     

Effective retrofitting of post-combustion CO2 capture to coal-fired power plants and insensitivity of CO2 abatement costs to base plant efficiency

Existing coal-fired power plants were not designed to be retrofitted with carbon dioxide post-combustion capture (PCC) and have tended to be disregarded as suitable candidates for carbon capture and storage on the grounds that such a retrofit would be uneconomical. Low plant efficiency and poor performance with capture compared to new-build projects are often cited as critical barriers to capture retrofit. Steam turbine retrofit solutions are presented that can achieve effective thermodynamic integration between a post-combustion CO₂ capture plant and associated CO₂ compressors and the steam cycle of an existing retrofitted unit for a wide range of initial steam turbine designs. The relative merits of these capture retrofit integration options with respect to flexibility of the capture system and solvent upgradability will be discussed. Provided that effective capture system integration can be achieved, it can be shown that the abatement costs (or cost per tonne of CO₂ to justify capture) for retrofitting existing units is independent of the initial plant efficiency. This then means that a greater number of existing power plants are potentially suitable for successful retrofits of post-combustion capture to reduce power sector emissions. Such a wider choice of retrofit sites would also give greater scope to exploit favourable site-specific conditions for CCS, such as ready access to geological storage.     

Optimal heat rejection pressure for transcritical CO2 refrigeration cycle with an expander

Heat rejection pressure plays an important role in designing a transcritical CO₂ refrigeration system, and it has an optimal value to maximize the system’s coefficient of performance (COP). With a thermodynamic simulation model, the optimal heat rejection pressure is studied in the paper for an expander cycle, as well as conventional throttle valve cycle. The effects of compressor efficiency, expander efficiency, gas cooler outlet temperature, and evaporation temperature on the optimal heat rejection pressure are analyzed. It is the first time for a transcritical CO₂ expander cycle that the optimal heat rejection pressure is correlated with the gas cooler outlet temperature and the evaporation temperature at given compressor efficiency and expander efficiency. The average deviation from the correlation to simulation results is less than 1.0%. The correlation provides a guideline to system development and performance optimization of a transcritical CO₂ expander cycle.     

Sorption-enhanced hydrogen production for pre-combustion CO2 capture: Thermodynamic analysis and experimental results

Hydrotalcite-based materials have been identified as suitable materials for high temperature (400 °C) adsorption of CO₂. In pre-combustion decarbonisation processes for natural gas based power cycles, it should be possible to use this material to improve conversions in the water-gas shift (WGS) and steam-reforming (SMR) reaction. The efficiencies for electricity production from natural gas have been calculated for some different system configurations, in which hydrotalcite-based material could be used. The calculated efficiency penalties ranged from 5.5 to 8.6 percentage points. The assumptions made in the system study have been tested on the laboratory scale. Hydrotalcite-based materials are found to be an excellent choice for use in the sorption-enhanced WGS reactor. The requirements for very low residual concentrations of CO₂ at 400 °C and large amounts of catalyst in the sorption-enhanced SMR reactor make its application less likely. Suggestions are made to how the SE-SMR could be improved.     

Life cycle assessment of a pulverized coal power plant with post-combustion capture, transport and storage of CO2

In this study the methodology of life cycle assessment has been used to assess the environmental impacts of three pulverized coal fired electricity supply chains with and without carbon capture and storage (CCS) on a cradle to grave basis. The chain with CCS comprises post-combustion CO₂ capture with monoethanolamine, compression, transport by pipeline and storage in a geological reservoir. The two reference chains represent sub-critical and state-of-the-art ultra supercritical pulverized coal fired electricity generation. For the three chains we have constructed a detailed greenhouse gas (GHG) balance, and disclosed environmental trade-offs and co-benefits due to CO₂ capture, transport and storage. Results show that, due to CCS, the GHG emissions per kWh are reduced substantially to 243 g/kWh. This is a reduction of 78 and 71% compared to the sub-critical and state-of-the-art power plant, respectively. The removal of CO₂ is partially offset by increased GHG emissions in up- and downstream processes, to a small extent (0.7 g/kWh) caused by the CCS infrastructure. An environmental co-benefit is expected following from the deeper reduction of hydrogen fluoride and hydrogen chloride emissions. Most notable environmental trade-offs are the increase in human toxicity, ozone layer depletion and fresh water ecotoxicity potential for which the CCS chain is outperformed by both other chains. The state-of-the-art power plant without CCS also shows a better score for the eutrophication, acidification and photochemical oxidation potential despite the deeper reduction of SO_x and NO_x in the CCS power plant. These reductions are offset by increased emissions in the life cycle due to the energy penalty and a factor five increase in NH₃ emissions.     

Off-design performance analysis of a transcritical CO2 Rankine cycle with LNG as cold source

The transcritical CO₂ Rankine cycle with liquefied natural gas (LNG) as cold source is a promising power system to utilize mid- and low-temperature heat source. Most previous works focused on thermodynamic and thermoeconomic analysis or optimization for the system. In this article, an off-design performance analysis for the system is conducted. An off-design mathematical model for the system is established to examine the variation of system performance with the variations of heat source mass flow rate and temperature. A modified sliding pressure regulation control strategy, which regulates turbine inlet pressure to keep the temperature difference between heat source temperature and turbine inlet temperature constant, is applied to control the system when off-design conditions happen. The results show that when the mass flow rate or the temperature of heat source is less or lower than that of design condition, both the net power output of system and the system exergy efficiency decrease, whereas when they are more or higher than the values of design condition, the net power output of system increases but the system exergy efficiency still decreases. In addition, both CO₂ turbine and NG turbine could almost keep the designed efficiency values under the applied control strategy.     

Quantitative evaluation of the chilled-ammonia process for CO2 capture using thermodynamic analysis and process simulation

There is strong world-wide interest in developing new and improved processes for post-combustion capture of CO₂, often using chemical absorption. Developers of new processes make positive claims for their proposals in terms of low energy consumption, but these are usually difficult to validate. This paper demonstrates that rigorous application of thermodynamic analysis and process simulation provides a powerful way to quantitatively estimate the energy requirements of CO₂-capture processes by applying the methodology to the analysis and evaluation of the chilled-ammonia process.     

Environmental impacts of absorption-based CO2 capture unit for post-combustion treatment of flue gas from coal-fired power plant

This study assesses potential environmental impacts of the absorption-based carbon dioxide (CO₂) capture unit that is integrated to coal-fired power plant for post-combustion treatment of flue gas. The assessment was performed by identifying potential pollutants and their sources as well as amounts of emissions from the CO₂ capture unit and also by reviewing toxicology, potential implications to human health and the environment, as well as the environmental laws and regulations associated with such pollutants. The assessment shows that, while offering a significant environmental benefit through a reduction of greenhouse gas emissions, the installation of CO₂ capture units for post-combustion treatment might induce unintentional and potential burdens to human health and the environment through four emission pathways, including treated gas, process wastes, fugitive emissions, and accidental releases. Such burdens nevertheless can be predetermined and properly mitigated through a well-established environmental management program and mitigation measures. Recommendations to minimize these impacts are provided in this paper.     

Worst case scenario study to assess the environmental impact of amine emissions from a CO2 capture plant

Use of amines is one of the leading technologies for post-combustion carbon dioxide capture from gas and coal-fired power plants. This study assesses the potential environmental impact of emissions to air that result from use of monoethanol amine (MEA) as an absorption solvent for the capture of carbon dioxide (CO₂). Depending on operation conditions and installed reduction technology, emissions of MEA to the air due to solvent volatility losses are expected to be in the range of 0.01–0.8 kg/tonne CO₂ captured. Literature data for human and environmental toxicity, together with atmospheric dispersion model calculations, were used to derive maximum tolerable emissions of amines from CO₂ capture. To reflect operating conditions with typical and with elevated emissions, we defined a scenario MEA-LOW, with emissions of 40 t/year MEA and 5 t/year diethyl amine (DEYA), and a scenario MEA-HIGH, with emissions of 80 t/year MEA and 15 t/year DEYA. Maximum MEA deposition fluxes would exceed toxicity limits for aquatic organisms by about a factor of 3–7 depending on the scenario. Due to the formation of nitrosamines and nitramines, the estimated emissions of DEYA are close to or exceed safety limits for drinking water and aquatic ecosystems. The “worst case” scenario approach to determine maximum tolerable emissions of MEA and other amines is in particular useful when both expected environmental loads and the toxic effects are associated with high uncertainties.     

Exergoeconomic and exergoenvironmental analyses of a combined cycle power plant with chemical looping technology

CO₂ capture and storage from energy conversion systems is one option for reducing power plant CO₂ emissions to the atmosphere and for limiting the impact of fossil-fuel use on climate change. Among existing technologies, chemical looping combustion (CLC), an oxy-fuel approach, appears to be one of the most promising techniques, providing straightforward CO₂ capture with low energy requirements.This paper provides an evaluation of CLC technology from an economic and environmental perspective by comparing it with to a reference plant, a combined cycle power plant that includes no CO₂ capture. Two exergy-based methods, the exergoeconomic and the exergoenvironmental analyses, are used to determine the economic and environmental impacts, respectively. The applied methods facilitate the iterative optimization of energy conversion systems and lead towards the improvement of the effectiveness of the overall plant while decreasing the cost and the environmental impact of the generated product. For the plant with CLC, a high increase in the cost of electricity is observed, while at the same time the environmental impact decreases.