Adsorption of carbon dioxide using impregnated activated carbon promoted by Zinc

The effect of impregnation of activated carbon with Cr₂O and Fe₂O₃ and promotion by Zn²⁺ on its adsorptive properties of carbon dioxide was studied using a volumetric adsorption apparatus at ambient temperature and low pressures. Slurry and solution impregnation methods were used to compare CO₂ capture capacity of the impregnated activated carbon promoted by Zinc. The obtained adsorption isotherms showed that amount of CO₂ adsorbed on the samples impregnated by Cr₂O was increased about 20% in compare to raw activated carbon. The results also showed that Fe₂O₃ was not an effective impregnating species for activated carbon modification. Moreover slurry impregnation method showed higher CO₂ adsorption capacity in comparison with solution impregnation method. Samples prepared by co-impregnation of two metal species showed more adsorption capacity than samples impregnated by just one metal species individually. Washing the impregnated samples by metal oxide resulted in 15% increase in CO₂ adsorption capacities of activated carbons which can be attributed to the metal oxides removal covering the adsorption surface. Decreasing impregnation temperature from 95 to 25 °C in solution method showed a significant increase in CO₂ adsorption capacity. Sips equation was found a suitable model fitting to the adsorption data in the range studied.     

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.     

Predictive tool for an accurate estimation of carbon dioxide transport properties

In the present work, simple-to-use predictive tool, which is simpler than current available models and involves a fewer number of parameters, requiring less complicated and shorter computations, is formulated to arrive at an appropriate estimation of the transport properties (namely viscosity and thermal conductivity) of carbon dioxide (CO₂) as a function of pressure and temperature. The correlation developed accurately works for temperatures between 260 and 450 K as well as pressures between 10 and 70 MPa which is the range of pressure that is widely considered in CO₂ sequestration. Results have been compared with the reported data and excellent agreement has been obtained between the predicted results and observed values. The average absolute deviations were found to be 1.1 and 1.3% for viscosity and thermal conductivity of carbon dioxide respectively. Proposed simple predictive tool and can be of immense practical value for the engineers to have a quick check on the transport properties (namely viscosity and thermal conductivity) of carbon dioxide at various temperatures and pressures without performing any experimental measurements. In particular, personnel dealing with regulatory bodies of greenhouse gas control and process industries would find the proposed approach to be user friendly involving transparent calculations with no complex expressions.     

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.     

Separation and recovery of carbon dioxide by a membrane flash process

A novel process for carbon dioxide (CO₂) separation, which was named a membrane flash process, was developed to realize an energy-saving technology and to substitute it for a conventional regenerator. The electric energy for CO₂ recovery in a membrane flash process using aluminum oxide and diethanolamine was lower than the thermal energy of the conventional chemical absorption process. Flashing at elevated temperature by the low temperature energy significantly reduced the electric energy and required much less membrane area. This process has potentiality of low cost capture of CO₂ when the low temperature energy, which is not available for other purposes, can be utilized to elevate flashing temperature.     

Exergy analysis as a tool for the integration of very complex energy systems: The case of carbonation/calcination CO2 systems in existing coal power plants

A common characteristic of carbon capture and storage systems is the important energy consumption associated with the CO₂ capture process. This important drawback can be solved with the analysis, synthesis and optimization of this type of energy systems. The second law of thermodynamics has proved to be an essential tool in power and chemical plant optimization. The exergy analysis method has demonstrated good results in the synthesis of complex systems and efficiency improvements in energy applications.In this paper, a synthesis of pinch analysis and second law analysis is used to show the optimum window design of the integration of a calcium looping cycle into an existing coal power plant for CO₂ capture. Results demonstrate that exergy analysis is an essential aid to reduce energy penalties in CO₂ capture energy systems. In particular, for the case of carbonation/calcination CO₂ systems integrated in existing coal power plants, almost 40% of the additional exergy consumption is available in the form of heat. Accordingly, the efficiency of the capture cycle depends strongly on the possibility of using this heat to produce extra steam (live, reheat and medium pressure) to generate extra power at steam turbine. The synthesis of pinch and second law analysis could reduce the additional coal consumption due to CO₂ capture 2.5 times, from 217 to 85 MW.     

A novel process integration,optimization and design approach for large-scale implementation of oxy-fired coal power plants with CO2 capture

The widespread use of fossil fuels within the current energy infrastructure is considered as the largest source of anthropogenic emissions of carbon dioxide, which is largely blamed for global warming and climate change. At the current state of development, the risks and costs of non-fossil energy alternatives, such as nuclear, biomass, solar, and wind energy, are so high that they cannot replace the entire share of fossil fuels in the near future timeframe. Additionally, any rapid change towards non-fossil energy sources, even if possible, would result in large disruptions to the existing energy supply infrastructure. As an alternative, the existing and new fossil fuel-based plants can be modified or designed to be either “capture” or “capture-ready” plants in order to reduce their emission intensity through the capture and permanent storage of carbon dioxide in geological formations. This would give the coal-fired power generation units the option to sustain their operations for longer time, while meeting the stringent environmental regulations on air pollutants and carbon emissions in years to come.Currently, there are three main approaches to capturing CO₂ from the combustion of fossil fuels, namely, pre-combustion capture, post-combustion capture, and oxy-fuel combustion. Among these technology options, oxy-fuel combustion provides an elegant approach to CO₂ capture. In this approach, by replacing air with oxygen in the combustion process, a CO₂-rich flue gas stream is produced that can be readily compressed for pipeline transport and storage. In this paper, we propose a new approach that allows air to be partially used in the oxy-fired coal power plants. In this novel approach, the air can be used to carry the coal from the mills to the boiler (similar to the conventional air-fired coal power plants), while O₂ is added to the secondary recycle flow as well as directly to the combustion zone (if needed). From a practical point of view, this approach eliminates problems with the primary recycle and also lessens concerns about the air leakage into the system. At the same time, it allows the boiler and its back-end piping to operate under slight suction; this avoids the potential danger to the plant operators and equipment due to possible exposure to hot combustion gases, CO₂ and particulates. As well, by integrating oxy-fuel system components and optimizing the overall process over a wide range of operating conditions, an optimum or near-optimum design can be achieved that is both cost-effective and practical for large-scale implementation of oxy-fired coal power plants.     

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.     

Electric Swing Adsorption for CO2 removal from flue gases

One of the most important sources of CO₂ emissions are the fossil-fuel fired plants for production of electricity. Removal of CO₂ from flue gas streams for further sequestration has been proposed by the International Panel on Climate Change experts as one of the most reliable solutions to mitigate anthropogenic greenhouse emissions. When natural gas is employed as fuel, the molar fraction of CO₂ in the flue gas is lower than 5% causing serious problems for capture. The purpose of this work is to present experimental validation of an Electric Swing Adsorption (ESA) technology that may be employed for carbon capture for low molar fractions of CO₂ in the flue gas streams. To improve energy utilization, an activated carbon honeycomb monolith with low electrical resistivity was employed as selective adsorbent. A mathematical model for this honeycomb is proposed as well as different ESA cycles for CO₂ capture.     

Integration of CO2 capture unit using single- and blended-amines into supercritical coal-fired power plants: Implications for emission and energy management

This work provides the essential information and approaches for integration of carbon dioxide (CO₂) capture units into power plants, particularly the supercritical type, so that energy utilization and CO₂ emissions can be well managed in the subject power plants. An in-house model, developed at the University of Regina, Canada, was successfully used for simulating a 500 MW supercritical coal-fired power plant with a post-combustion CO₂ capture unit. The simulations enabled sensitivity and parametric study of the net efficiency of the power plant, the coal consumption rate, and the amounts of CO₂ captured and avoided. The parameters of interest include CO₂ capture efficiency, type of coal, flue gas delivery scheme, type of amine used in the capture unit, and steam pressure supplied to the capture unit for solvent regeneration. The results show that the advancement of MEA-based CO₂ capture units through uses of blended monoethanolamine–methyldiethanolamine (MEA–MDEA) and split flow configuration can potentially make the integration of power plant and CO₂ capture unit less energy intensive. Despite the increase in energy penalty, it may be worth capturing CO₂ at a higher efficiency to achieve greater CO₂ emissions avoided. The flue gas delivery scheme and the steam pressure drawn from the power plant to the CO₂ capture unit should be considered for process integration.     

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

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

Low-energy sodium hydroxide recovery for CO2 capture from atmospheric air—Thermodynamic analysis

To reduce the risks of climate change, atmospheric concentrations of greenhouse gases must be lowered. Direct capture of CO₂ from ambient air, “air capture”, might be one of the few methods capable of systematically managing dispersed emissions. The most commonly proposed method for air capture is a wet scrubbing technique which absorbs CO₂ in an alkaline absorbent, i.e. sodium hydroxide producing an aqueous solution of sodium hydroxide and sodium carbonate. In most of the previous works it was assumed that the absorbent would be regenerated and CO₂ liberated from the alkaline carbonate solution using a lime and calcium carbonate causticization cycle.We describe a novel technique for recovering sodium hydroxide from an aqueous alkaline solution of sodium carbonate and present an end-to-end energy and exergy analysis. In the first step of the recovery process, anhydrous sodium carbonate is separated from the concentrated sodium hydroxide solution using a two-step precipitation and crystallization process. The anhydrous sodium carbonate is then causticized using sodium tri-titanate. The titanate direct causticization process has been of interest for the pulp and paper industry and has been tested at lab- and pilot-scale. In the causticization process, sodium hydroxide is regenerated and carbon dioxide is liberated as a pure stream, which is compressed for use or disposal. The technique requires ～50% less high-grade heat than conventional causticization and the maximum temperature required is reduced by at least 50 °C. This titanate cycle may allow a substantial reduction in the overall cost of direct air capture.     

A statistical analysis of the carbon dioxide capture process

Post combustion carbon dioxide (CO₂) capture is one of the most commonly adopted technologies for reducing industrial CO₂ emissions, which is now an important goal given the widespread concern over global warming. Research on amine-based CO₂ capture has mainly focused on improving effectiveness and efficiency of the CO₂ capture process. Our research work focuses on studying the relationships among the significant parameters influencing CO₂ production because an enhanced understanding of the intricate relationships among the parameters involved in the process is critical for improving efficiency of the CO₂ capture process. This paper presents a statistical study that explores the relationships among parameters involved in the amine-based post combustion CO₂ capture process at the International Centre for CO₂ Capture (ITC) located in Regina, Saskatchewan of Canada. A multiple regression technique has been applied for analysis of data collected at the CO₂ capture pilot plant at ITC. The parameters have been carefully selected to avoid issues of multicollinearity, and four mathematical models among the key parameters identified have been developed. The models have been tested, and accuracy of the models is found to be satisfactory. The models developed in this study describe part of the CO₂ capture process and can help to predict performance of the CO₂ capture process at ITC under different conditions. Some results from a preliminary validation process will also be presented.     

CO2 removal using membrane gas absorption

The objective of this study is to investigate the potential process for the removal of carbon dioxide (CO₂) from flue gas using fundamental membrane contactor, which is a membrane gas absorption (MGA) system. The experiments consisted of microporous polyvinylidenefluoride (PVDF) flat sheet membrane with 0.1 μm (as module I) and 0.45 μm (as module II) pore size. 2-Amino-2-methyl-1-propanol (AMP) solution was employed as the liquid absorbent. The effect of AMP concentration was studied with variation in the range 1–5 M. In addition, the experiments were carried out with 10%, 20%, 30% and 40% gas ratio of CO₂ to N₂ and pure CO₂ as well. Through contact angle measurement, membranes for module I and module II were obtained with CA values of around 130.25° and 127.77°, respectively. The mass transfer coefficients for module II are lower than those of module I for 1–5 M of AMP. Furthermore, the increase in CO₂ concentration in the feed gas stream enhanced the CO₂ flux as the driving force of the system was increased in sequence from 1 M to 5 M of AMP. However, after the particular percentage (40%) of CO₂ inlet concentration, the CO₂ fluxes seem saturated. The combination of AMP as liquid absorbent and PVDF microporous membrane in MGA system has shown the potential to remove the CO₂ from flue gas. In addition, the higher AMP concentration gave higher mass transfer coefficient at low liquid flow rates.     

Steam demand reduction of water–gas shift reaction in IGCC power plants with pre-combustion CO2 capture

This paper presents the results of system assessments that were conducted to compare conventional and advanced water–gas shift reactor sections. The latter are specifically tailored for Integrated Gasification Combined Cycles (IGCC) power plants with pre-combustion CO₂ capture. The advanced shift reactor section comprises four staged reactors with distributed feeds of synthesis gas and quench water in between the reactors. Conventional shift reactor sections consist of two sequential reactors with intermediate cooling, where the entire synthesis gas stream passes both reactors.The advanced shift reactor section reduces the steam requirement of the water–gas shift reaction up to 70% in comparison with conventional configurations, at carbon dioxide capture ratios of approximately 85%. This reduction allows for lower electric efficiency penalties, thus higher net electric outputs for IGCC power plants with CO₂ capture. For each case, the CO₂ capture ratio was optimised for the lowest specific lost work per amount of captured CO₂. Both the number of reactors and the total catalyst volume are higher for the advanced shift reactor sections, resulting in increased capital expenses. In case of four staged reactors, the additional expenses are expected to be outperformed by the increased revenues associated with the higher net electric output.     

Performance of amine-multilayered solid sorbents for CO2 removal: Effect of fabrication variables

The emission of fossil fuel carbon dioxide (CO₂) to the atmosphere is implicated as the predominant cause of global climate change; therefore, advanced CO₂ capture technologies are of the utmost importance. In this study, innovative amine-multilayered sorbents were fabricated using layer-by-layer (LbL) nanoassembly technology via alternate deposition of a CO₂-adsorbing amine polymer (e.g. polyethylenimine or PEI) and an oppositely-charged polymer (e.g. polystyrene sulfonate or PSS). We found that the developed sorbents could be used for CO₂ capture and that LbL nanoassembly allows us to engineer their CO₂ capture performance through the fabrication variables (e.g. deposition polymers, deposition media, and number of bilayers). PEI/PSS was found to be the best polymer combination for developing sorbents with relatively high CO₂ capture capacity. The amine-multilayered solid sorbents possessed fine microstructures and may have similar polymer deposition within and on the surface of solid sorbents. These amine-multilayered sorbents had much faster CO₂ desorption rates compared to sorbents prepared using the current PEI-impregnation approach. Such fast CO₂ desorption could make sorbents a good option for CO₂ removal from power plants and even the atmosphere.     

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 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.     

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.