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%.     

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.     

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.     

Ionic liquids for post-combustion CO2 absorption

The present work is a study to evaluate ionic liquids as a potential solvent for post-combustion CO₂ capture. In order to enhance the absorption performance of a CO₂ capture unit, different ionic liquids have been designed and tested. The main goal was to get a comparison between a reference liquid and selected ionic liquids. As the reference, a solution of 30 w% monoethanolamine (MEA) and water was used. A large range of different pure and diluted ionic liquids was tested with a special screening process to gain general information about the CO₂ absorption performance. Based on these results, a 60 w% ionic liquid solution in water was selected and the vapour–liquid equilibrium was measured experimentally between 40 °C and 110 °C. From these curves the enthalpy of absorption for capturing CO₂ into the ionic liquid was determined. With these important parameters one is able to calculate the total energy demand for stripping of CO₂ from the loaded solvent for comparison of the ionic liquid based solvent with the reference MEA solvent. The energy demand of this 60 w% ionic liquid is slightly lower than that of the reference solution, resulting in possible energy savings between 12 and 16%.     

Hollow fiber membrane separation process in the presence of gaseous and particle impurities for post-combustion CO2 capture

The membrane separation process for CO₂ capture can be interfered by the gaseous components and the fine particles in flue gas, especially in desulfurized flue gas. In this work, the pint-sized Polyimide(PI) hollow fiber membrane contactors were self-packed to investigate the membrane CO₂ separation from flue gas containing fine particles and gaseous contaminants (SO₂,SO₃,H₂O). First, the effects of SO₂, SO₃, water vapor, and gypsum particles on the CO₂ capture were studied independently and synergistically. The results showed that the effect of SO₂ on the membrane separation properties is indistinctive; however, the membrane performance was damaged seriously with the addition of SO₃. The high humidity promoted the CO₂ separation initially before inhibiting the PI membrane performance. Moreover, the decrease of the CO₂/N₂ selectivity and the permeation rate were accelerated with the coexistence of SO₂. The membrane performance showed an obvious deterioration in the presence of gypsum particles, with a 21% decrease in the CO₂/N₂ selectivity and 51% decrease in the permeation rate. Furthermore, the gypsum particles exerted dramatic damage. Under the WFGD conditions, the combined effects of SO₂, water vapor, and the gypsum particles influenced the stability of the membrane significantly. This tendency is mainly attributed to the deposition of fine particles and aerosol on the membrane surface, which occupied the effective area and enhanced the mass transfer resistance. This study of impurities’ influence could play an important role in further industrial application of membrane CO₂ capture.     

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.     

A short-cut method for assessing absorbents for post-combustion carbon dioxide capture

A short-cut method for the estimation of the minimum regeneration energy and optimum solvent flow rate in post-combustion carbon dioxide capture by absorption is presented. It is developed for comparing solvents of which only little thermo-physical data is known. The closed absorber–desorber cycle is described by an equilibrium stage model (modified Kremser equation with discretized equilibrium curves). The method can be implemented in any mathematical toolbox or as stand-alone solution. The only required input is the solubility data at absorber and desorber conditions, the heat of absorption and heat capacities. The caloric data may be estimated. The method was applied to monoethanolamine (MEA) and two solvents from the EU-project CASTOR. Comparisons with experimental results from pilot-plant studies with MEA show that the method, despite its simplicity, gives reasonable results. The method should also be useful in other applications where absorbents, of which only little data is available, need to be screened.     

Chilled ammonia process for CO2 capture

The chilled ammonia process absorbs the CO₂ at low temperature (2–10 °C). The heat of absorption of carbon dioxide by ammonia is significantly lower than for amines. In addition, degradation problems can be avoided and a high carbon dioxide capacity is achieved. Hence, this process shows good perspectives for decreasing the heat requirement. However, a scientific understanding of the processes is required. The thermodynamic properties of the NH₃–CO₂–H₂O system were described using the extended UNIQUAC electrolyte model developed by Thomsen and Rasmussen in a temperature range from 0 to 110 °C and pressure up to 100 bars. The results show that solid phases consisting of ammonium carbonate and bicarbonate are formed in the absorber. The heat requirements in the absorber and in the desorber have been studied. The enthalpy calculations show that a heat requirement for the desorber lower than 2 GJ/ton CO₂ can be reached.     

Oxygen supply for oxyfuel CO2 capture

This paper presents the results of a study to develop Air Products’ air separation unit (ASU) offerings for oxyfuel coal CO₂ capture projects. A scalable “reference plant” concept is described to match particular sizes of power generation equipment, taking into account factors such as safety, reliability, operating flexibility, efficiency, and low capital cost. We describe the selection of a process cycle to exploit the low purity requirements, as well as the options for compression machinery and drivers as the scale of the plant increases and the sizes of referenced equipment limit the possibilities. We also explore integration with other elements of the system, such as preheating condensate or heating and expanding pressurised nitrogen. In addition, we consider how the ASU affects the flexibility of the oxyfuel system and discuss how its power consumption can be reduced during periods of high power demand. Finally, the advantages and disadvantages of different execution strategies for air separation unit projects are discussed, as well as alternative commercial models for the supply of oxygen.     

Novel lithium-based sorbents from fly ashes for CO2 capture at high temperatures

In this work several Li₄SiO₄-based sorbents from fly ashes for CO₂ capture at high temperatures have been developed. Three fly ash samples were collected and subjected to calcination at 950 °C in the presence of Li₂CO₃. Both pure Li₄SiO₄ and fly ash-based sorbents were characterised and tested for CO₂ sorption at different temperatures between 400 and 650 °C and adding different amounts of K₂CO₃ (0–40 mol%). To examine the sorbents performance, multiple CO₂ sorption/desorption cycles were carried out. The temperature and the presence of K₂CO₃ strongly affect the CO₂ sorption capacity for the sorbents prepared from fly ashes. When the sorption temperature increases by up to 600 °C both the CO₂ sorption capacity and the sorption rate increase significantly. Moreover when the amount of K₂CO₃ increases, the CO₂ sorption capacity also increases. At optimal experimental conditions (600 °C and 40 mol% K₂CO₃), the maximum CO₂ sorption capacity for the sorbent derived from fly ash was 107 mg CO₂/g sorbent. The Li₄SiO₄-based sorbents can maintain its original capacity during 10 cycle processes and reach the plateau of maximum capture capacity in less than 15 min, while pure Li₄SiO₄ presents a continual upward tendency for the 15 min of the capture step and attains no equilibrium capacity.     

Amine volatility in CO2 capture

Amine volatility is a key screening criterion for amines to be used in CO₂ capture. Excessive volatility may result in significant economic losses and environmental impact. It also dictates the capital cost of the water wash. This paper reports measured amine volatility in 7 m MEA (monoethanolamine), 8 m PZ (piperazine), 7 m MDEA (n-methyldiethanolamine)/2 m PZ (piperazine), 12 m EDA (ethylenediamine), and 5 m AMP (2-amino-2-methyl-1-propanol) at 40–60 °C with lean and rich loadings giving CO₂ partial pressures of 0.5 and 5 kPa at 40 °C. The amine concentrations were chosen to maximize CO₂ capture capacity at acceptable viscosity. At the lean loading condition (where volatility is of greatest interest), the amines are ranked in order of increasing volatility: 7 m MDEA/2 m PZ (6/2 ppm), 8 m PZ (8 ppm), 12 m EDA (9 ppm), 7 m MEA (31 ppm), and 5 m AMP (112 ppm). The apparent amine partial molar excess enthalpies in these systems were estimated to range from ～10 to 87 kJ/mol of amine.     

Comparative study of the heats of absorption of post-combustion CO2 absorbents

Heats of absorption of CO₂ with different solvents were measured in this work in a commercially available reaction calorimeter CPA-122 (Chemisens AS, Sweden) as function of temperature, loading and solvent composition over the temperature range from 40 to 120 °C. Studied amines include primary amines (monoethanolamine and 2-amino-2-methyl-1-propanol), tertiary amines (N-methyldiethanolamine and N,N-diethylethanolamine), diamines (1-(2-aminoethyl)-aminoethanol and N-methyl-1,3-propanediamine), triamine (diethylenetriamine), and cyclic amine (piperazine). Combinations of these amines and also mixtures of potassium carbonate and piperazine were tested. Experimental heats of absorption of CO₂ with these systems are compared.     

CO2 capture for refineries,a practical approach

This paper evaluates the opportunities and associated costs for post-combustion capture at a world-scale complex refinery. It is concluded that it is technically feasible to apply post-combustion capture at such a refinery. The costs for capture and sequestration from a gasifier are calculated to be lowest at about 30 Euro per ton; this process currently already produces a concentrated CO₂ stream. Next, the CO₂ source most suited for capture appears to be a combined stack, but there are a number of other sources that may be targeted at comparable costs. In total these sources may form about 40% of the overall refinery emissions. Our evaluations show the costs of capture from such sources based on available amine technology will be in the range of 90–120 Euro per ton, which is about 3–4 times higher than the current carbon trading values. The capture of CO₂ from a large amount of smaller CO₂ sources will bring along even much higher costs. A high-level study of the CO₂ emissions profile of a number of Shell refineries shows that, typically, up to 50% of the emitted CO₂ may be captured at similar costs. About 10–20% of concentrated CO₂ associated with hydrogen manufacturing may be captured at lower costs. The remainder of emitted dilute CO₂ will bring along significantly higher costs. Based on this study, it is concluded for the justification of the implementation of post-combustion capture at refineries, either a significant increase in carbon trading values, mandatory regulations, or a major technological break-through is required.     

CO2 capture from hot stove gas in steel making process

The capture of CO₂ from a hot stove gas in steel making process containing 30 vol% CO₂ by chemical absorption in a rotating packed bed (RPB) was studied. The RPB had an inner diameter of 7.6 cm, an outer diameter of 16 cm, and a height of 2 cm. The aqueous solutions containing 30 wt% of single and mixed monoethanolamine (MEA), 2-(2-aminoethylamino)ethanol (AEEA), and piperazine (PZ) were used. The CO₂ capture efficiency was found to increase with increasing temperature in a range of 303–333 K. It was also found to be more dependent on gas and liquid flow rates but less dependent on rotating speed when the speed was higher than 700 rpm. The obtained results indicated that the mixed alkanolamine solutions containing PZ were more effective than the single alkanolamine solutions. This was attributed to the highest reaction rate of PZ with CO₂. A higher portion of PZ in the mixture was more favorable to CO₂ capture. The highest gas flow rates allowed to achieve a desired CO₂ capture efficiency and the correspondent height of transfer unit (HTU) were determined at different aqueous solution flow rates. Because all the 30 wt% single and mixed alkanolamine solutions could result in a HTU less than 5.0 cm at a liquid flow rate of 100 mL/min, chemical absorption in a RPB instead of a packed bed adsorber is therefore suggested to capture CO₂ from the flue gases in steel making processes.     

Minimising the regeneration heat duty of post-combustion CO2 capture by wet chemical absorption: The misguided focus on low heat of absorption solvents

An ideal solvent for CO₂ capture by chemical absorption has to meet a number of requirements, such as high CO₂ capacity, high rate of reaction, low costs, low corrosive behaviour, low degradation and low vapour pressure; above all, it has to show a low regeneration heat duty. This heat can be approximated as the sum of three terms: the sensible heat to raise the solvent from absorber to desorber temperature, the heat of evaporation required to produce the stripping steam in the reboiler, and the heat necessary to desorb the CO₂ from the solution (heat of absorption).Many solvent screening studies focus almost exclusively on solvents that show a low heat of absorption. In these studies, the strong dependence of the three contributors to the overall regeneration heat duty on the chosen process parameters and on one another are often neglected.This work explains why the focus on solvents with a low heat of absorption, without considering the overall process, is not sufficient in quantifying the energy performance of alternative solvents. By using thermodynamic interrelations and underpinned by process simulations it is shown that operating parameters of the process, in particular the desorber pressure, must be taken into consideration in the evaluation of new solvents.     

Modeling CO2 capture with aqueous monoethanolamine

Hilliard completed several thermodynamic models in Aspen Plus^® for modeling CO₂ removal with amine solvents, including MEA–H₂O–CO₂. This solvent was selected to make a system model for CO₂ removal by absorption/stripping. Both the absorber and the stripper used RateSep? to rigorously calculate mass transfer rates. The accuracy of the new model was assessed using a recent pilot plant run with 35 wt.% (9 m) MEA. Absorber loading and removal were predicted within 6%, and the temperature profile was approached within 5 °C. An average 3.8% difference between measured and calculated values was achieved in the stripper. A three-stage flash configuration which efficiently utilizes solar energy was developed. It reduces energy use by 6% relative to a simple stripper. Intercooling was used to reach 90% removal in the absorber at these optimized conditions.     

Techno-economic study of CO2 capture from natural gas based hydrogen plants

Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas (SMR). The future expansion of oil sands operations is likely to quadruple the demand of H₂ for oil sand operations in the next decade.This paper presents modified process schemes that capture CO₂ at minimum energy penalty in modern SMR plants. The approach is to simulate a base case H₂ plant without CO₂ capture and then look for the best operating conditions that minimize the energy penalty associated with CO₂ capture while maximizing H₂ production. The two CO₂ capture schemes evaluated in this study include a membrane separation process and the monoethanolamine (MEA) absorption process. A low energy penalty is observed when there is lower CO₂ production and higher steam production. The process simulation results show that the H₂ plant with CO₂ capture has to be operated at lower steam to carbon ratio (S/C), higher inlet temperature of the SMR and lower inlet temperatures for the water gas-shift (WGS) converters to attain lowest energy penalty. Also it is observed that both CO₂ capture processes, the membrane process and the MEA absorption process, are comparable in terms of energy penalty and CO₂ avoided when both are operated at conditions where lowest energy penalty exists.     

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.     

Integration of post-combustion capture and storage into a pulverized coal-fired power plant

Post-combustion CO₂ capture and storage (CCS) presents a promising strategy to capture, compress, transport and store CO₂ from a high volume–low pressure flue gas stream emitted from a fossil fuel-fired power plant. This work undertakes the simulation of CO₂ capture and compression integration into an 800 MW_e supercritical coal-fired power plant using chemical process simulators. The focus is not only on the simulation of full load of flue gas stream into the CO₂ capture and compression, but also, on the impact of a partial load. The result reveals that the energy penalty of a low capture efficiency, for example, at 50% capture efficiency with 10% flue gas load is higher than for 90% flue gas load at the equivalent capture efficiency by about 440 kWh_e/tonne CO₂. The study also addresses the effect of CO₂ capture performance by different coal ranks. It is found that lignite pulverized coal (PC)-fired power plant has a higher energy requirement than subbituminous and bituminous PC-fired power plants by 40.1 and 98.6 MW_e, respectively. In addition to the investigation of energy requirement, other significant parameters including energy penalty, plant efficiency, amine flow rate and extracted steam flow rate, are also presented. The study reveals that operating at partial load, for example at half load with 90% CO₂ capture efficiency, as compared with full load, reduces the energy penalty, plant efficiency drop, amine flow rate and extracted steam flow rate by 9.9%, 24.4%, 50.0% and 49.9%, respectively. In addition, the effect of steam extracted from different locations from a series of steam turbine with the objective to achieve the lowest possible energy penalty is evaluated. The simulation shows that a low extracted steam pressure from a series of steam turbines, for example at 300 kPa, minimizes the energy penalty by up to 25.3%.