CO2 capture by adsorption: Materials and process development

Vacuum swing adsorptive (VSA) capture of CO₂ from flue gas and related process streams is a promising technology for greenhouse gas mitigation. Although early reports suggested that VSA was problematic and expensive, through the application of more logical process configurations that are appropriately coupled to the composition of the feed and product gas streams, we can now refute this early assertion. Improved cycle designs coupled with tighter temperature control are also helping to optimise performance for CO₂ separation. Simultaneously, new adsorbent materials are being developed. These separate CO₂ by selective (acid-base) reaction with surface bound amine groups (chemisorption), rather than on the basis of non-bonding interactions (physisorption). This report describes some of these recent developments from our own laboratories and points to synergies that are anticipated as a result of combining these improvements in adsorbent properties and VSA process cycles.     

Continuous operation of the potassium-based dry sorbent CO2 capture process with two fluidized-bed reactors

The dry sorbent CO₂ capture process is an advanced concept to efficiently remove CO₂ from flue gas with two fluidized-bed reactors. This paper summarizes the results of performance of the two fluidized-bed reactors in the continuous solid circulation mode to investigate the feasibility of using potassium carbonate-based solid sorbent (Sorb KX35). The parameters such as gas velocity, solid circulation, carbonation temperature, and water vapor content were investigated during several continuous operations of two fluidized-bed reactors. The CO₂ removal increased as gas velocity was decreased and as solid circulation rate was increased. The CO₂ removal ranged from 26% to 73% was rather sensitive to the water vapor content among other parameters. A 20 h continuous operation conducted in a bench scale fast fluidized-bed reactor system indicated that the spray-dried potassium-based sorbent, Sorb KX35 having superior attrition resistance and high bulk density, had a promising CO₂ removal capacity of 50–73% at steady state and was able to regenerate and reuse. The results from this work are good enough to prove the concept of the dry sorbent CO₂ capture process to be one of viable methods for capturing CO₂ from dilute flue gas of fossil fuel-fired power plants.     

Conceptual design of a three fluidised beds combustion system capturing CO2 with CaO

In this work, the Aspen Hysys conceptual design of a new process for energy generation at large scale with implicit CO₂ capture is presented. This process makes use of the CaO capability for CO₂ capture at high temperature and the possibility of regenerating this sorbent working in interconnected fluidised bed reactors operating at different temperatures. The proposed process has the advantage of producing power with minimum CO₂ emissions and very low energy penalties compared with similar air-based combustion power plants. In this system, five main parts can be distinguished: the combustor where coal is burnt with air, the calciner where the fresh and the recycled CaCO₃ is calcined, the carbonator where the CO₂ produced in the combustor is captured, the supercritical steam cycle and the CO₂ compression system. In this arrangement, the three fluidised bed reactors are interconnected in such a way that it is possible to perform the CaCO₃ calcination at a temperature of 950 °C with the energy transported by a hot solid stream produced in the circulating fluidised bed combustor operating at 1030 °C. The stream rich in CaO produced in the calciner is split into three parts. One of them is transported to the carbonator operating at 650 °C where most of the CO₂ in the flue gas produced in the combustor is captured. The second one is sent to the combustor, where it is heated up and used as energy carrier. The third solid stream that leaves the calciner is a purge in order to maintain the capture system activity and to avoid inert material accumulation. Because of the high temperatures involved in all the system, it is possible to recover most of the energy in the fuel and to produce power in a supercritical steam cycle. A case study is presented and it is demonstrated that under these operating conditions, 90% CO₂ capture efficiency can be achieved with no energy penalty further than the one originated in the CO₂ compression system.     

Experimental validation of in situ CO2 capture with CaO during the low temperature combustion of biomass in a fluidized bed reactor

A novel concept for capturing CO₂ from biomass combustion using CaO as an active solid sorbent of CO₂ is discussed and experimentally tested. According to the CaO/CaCO₃ equilibrium, if a fuel could be burned at a sufficiently low temperature (below 700 °C) it would be possible to capture CO₂ “in situ” with the CaO particles at atmospheric pressure. A subsequent step involving the regeneration of CaCO₃ in a calciner operating at typical conditions of oxyfired-circulating fluidized combustion would deliver the CO₂ ready for purification, compression and permanent geological storage. Several series of experiments to prove this concept have been conducted in a 30 kW interconnected fluidized bed test facility at INCAR-CSIC, made up of two interconnected circulating fluidized bed reactors, one acting as biomass combustor-carbonator and the other as air-fired calciner (which is considered to yield similar sorbent properties than those of an oxyfired calciner). CO₂ capture efficiencies in dynamic tests in the combustor-carbonator reactor were measured over a wide range of operating conditions, including different superficial gas velocities, solids circulation rates, excess air above stoichiometric, and biomass type (olive pits, saw dust and pellets). Biomass combustion in air is effective at temperatures even below the 700 °C, necessary for the effective capture of CO₂ by carbonation of CaO. Overall CO₂ capture efficiencies in the combustor-carbonator higher than 70% can be achieved with sufficiently high solids circulation rates of CaO and solids inventories. The application of a simple reactor model for the combined combustion and CO₂ capture reactions allows an efficiency factor to be obtained from the dynamic experimental test that could be valuable for scaling up purposes.     

CO2 capture from power plants: Part II. A parametric study of the economical performance based on mono-ethanolamine

While the demand for reduction in CO₂ emission is increasing, the cost of the CO₂ capture processes remains a limiting factor for large-scale application. Reducing the cost of the capture system by improving the process and the solvent used must have a priority in order to apply this technology in the future. In this paper, a definition of the economic baseline for post-combustion CO₂ capture from 600 MW_e bituminous coal-fired power plant is described. The baseline capture process is based on 30% (by weight) aqueous solution of monoethanolamine (MEA). A process model has been developed previously using the Aspen Plus simulation programme where the baseline CO₂-removal has been chosen to be 90%. The results from the process modelling have provided the required input data to the economic modelling. Depending on the baseline technical and economical results, an economical parameter study for a CO₂ capture process based on absorption/desorption with MEA solutions was performed.Major capture cost reductions can be realized by optimizing the lean solvent loading, the amine solvent concentration, as well as the stripper operating pressure. A minimum CO₂ avoided cost of € 33 tonne⁻¹ CO₂ was found for a lean solvent loading of 0.3 mol CO₂/mol MEA, using a 40 wt.% MEA solution and a stripper operating pressure of 210 kPa. At these conditions 3.0 GJ/tonne CO₂ of thermal energy was used for the solvent regeneration. This translates to a € 22 MWh⁻¹ increase in the cost of electricity, compared to € 31.4 MWh⁻¹ for the power plant without capture.     

CO2 capture from power plants: Part I. A parametric study of the technical performance based on monoethanolamine

Capture and storage of CO₂ from fossil fuel fired power plants is drawing increasing interest as a potential method for the control of greenhouse gas emissions. An optimization and technical parameter study for a CO₂ capture process from flue gas of a 600 MWe bituminous coal fired power plant, based on absorption/desorption process with MEA solutions, using ASPEN Plus with the RADFRAC subroutine, was performed. This optimization aimed to reduce the energy requirement for solvent regeneration, by investigating the effects of CO₂ removal percentage, MEA concentration, lean solvent loading, stripper operating pressure and lean solvent temperature.Major energy savings can be realized by optimizing the lean solvent loading, the amine solvent concentration as well as the stripper operating pressure. A minimum thermal energy requirement was found at a lean MEA loading of 0.3, using a 40 wt.% MEA solution and a stripper operating pressure of 210 kPa, resulting in a thermal energy requirement of 3.0 GJ/ton CO₂, which is 23% lower than the base case of 3.9 GJ/ton CO₂. Although the solvent process conditions might not be realisable for MEA due to constraints imposed by corrosion and solvent degradation, the results show that a parametric study will point towards possibilities for process optimisation.     

Optimization of a membrane process for CO2 capture in the steelmaking industry

Three different types of membranes were experimentally evaluated for CO₂ recovery from blast furnace effluents: semi-commercial adsorption selective carbon membranes, in-house tailored carbon molecular sieving membranes, and fixed site carrier (FSC) membranes with amine groups in the polymer backbone for active transport of CO₂. In the single gas experiments the FSC membranes showed superior selectivity for CO₂ over the other relevant gases (CO, N₂ and H₂) and high CO₂ permeance (productivity). In addition, it is easy to process and handle, relatively inexpensive to produce and the water in the feed gas is an advantage rather than a problem, since the membrane must be humidified during operation. Based on these experiments a simulation study of a full scale process was performed. The technology showed notable low energy cost, even when converted to the thermal equivalent. Total costs for the CO₂ recovery unit (CO₂ prepared for pipeline transport) were estimated to be in the range 15.0–17.5 €/tonnes CO₂.     

Hydrate formation during CO2 transport: Predicting water content in the fluid phase in equilibrium with the CO2-hydrate

In order to evaluate the risk of hydrate formation in CO₂ transport one has to be able to predict the water content in the fluid phase in equilibrium with the CO₂-hydrate. A literature review has identified some knowledge gaps, for example, there are no results available at temperatures lower than 243.15 K (?30 °C); and none of the models found in literature predicts the water content with high accuracy. A model based on equality of water fugacity in fluid and hydrate phase is presented here and used for the predictions of water content in equilibrium with hydrates. Although this model gives better accuracy in the overall temperature and pressure ranges of measurements than the models found in the literature, it is not accurate enough to satisfy the requirements of CO₂ transport. The simulation results also show that it is possible to form hydrate at low water content, such as x_w = 50 vppm, if temperature is low enough. In order to verify the results and improve the model accuracy further, more experimental data in a larger temperature and pressure region are required.     

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.     

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.     

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.     

Comparison of adsorption models in reservoir simulation of enhanced coalbed methane recovery and CO2 sequestration in coal

Coalbed methane is an important resource of energy. Meanwhile CO₂ sequestration in coal is a potential management option for greenhouse gas emissions. An attractive aspect to this process is that CO₂ is adsorbed to the coal, reducing the risk of CO₂ migration to the surface. Another aspect to this is that the injected CO₂ could displace adsorbed methane leading to enhanced coalbed methane recovery. Therefore, in order to understand gas migration within the reservoir, mixed-gas adsorption models are required. Moreover, coal reservoir permeability will be significantly affected by adsorption-induced coal swelling during CO₂ injection. Coal swelling is directly related to reservoir pressure and gas content which is calculated by adsorption models in reservoir simulation. Various models have been studied to describe the pure- and mixed-gas adsorption on coal. Nevertheless, only the Langmuir and Extended Langmuir models are usually applied in coal reservoir simulations. This paper presents simulation work using several approaches to representing gas adsorption, implemented into the coal seam gas reservoir simulator SIMED II. The adsorption models are the Extended Langmuir model (ELM), the Ideal Adsorbed Solution (IAS) model and the Two-Dimensional Equation of State (2D EOS). The simulations based on one Australian and one American coal sample demonstrated that (1) the Ideal Adsorbed Solution model, in conjunction with Langmuir model as single-component isotherm, shows similar simulation results as the ELM for both coals, with the IAS model representing the experimental adsorption data more accurately than the ELM for one coal and identically with the ELM for the other coal; (2) simulation results using the 2D EOS, however, are significantly different to the ELM or IAS model for both coal samples. The magnitude of the difference is also dependent on coal swelling and the well operating conditions, such as injection pressure.     

Study of individual reactions of the sour compression process for the purification of oxyfuel-derived CO2

Following the feasibility study of sour compression process as a novel purification method of producing NO_x-free, SO₂-free oxyfuel-derived CO₂ using actual fluegas, in this paper, we present the study of the individual reactions taking place in the process in a controlled environment. We have previously showed that an increase of NO/NO₂ concentration in the inlet stream is beneficial for SO₂ removal as NO₂ promotes SO₂ oxidation and the further removal as liquid acid. In this study we show that the reaction SO₂ + NO₂ → SO₃ + NO does not take place significantly in the absence of liquid water at a range of conditions relevant to the sour compression process. When liquid water is present, SO₂ is oxidised by NO₂ regenerating NO with the rate of conversion of SO₂ being dependent on the acid concentration in the liquid. The formation of small liquid droplets where very low levels of pH (?0) can be reached is shown to be of great importance to the SO₂ + NO₂ conversion process.     

Evaluating the impact of fractures on the performance of the In Salah CO2 storage site

The In Salah Gas Joint Venture CO₂ storage project has been in operation in Algeria since 2004 and is currently the world's largest onshore CO₂ storage project. CO₂ is injected into the saline aquifer of a gas reservoir several kilometres away from the gas producers. Current focus in the project is on implementing a comprehensive monitoring strategy and modelling the injection behaviour in order to ensure and verify safe long-term storage. A key part of this effort is the understanding of the processes involved in CO₂ migration within relatively low-permeability sandstones and shales influenced by fractures and faults. We summarise our current understanding of the fault and fracture pattern at this site and show preliminary forecasts of the system performance using discrete fracture models and fluid flow simulations. Despite evidence of fractures at the reservoir/aquifer level, the thick mudstone caprock sequence is expected to provide an effective flow and mechanical seal for the storage system; however, quantification of the effects of fracture flow is essential to the site verification.     

Optimizing process parameters for the adsorption of phosphorus from synthetic wastewater on coconut shell based activated carbon

Activated carbon was prepared from coconut shell, an agricultural waste, for the removal of phosphorus from synthetic phosphorus‐containing wastewater. The activated carbon obtained from the coconut shell was characterized using Fourier‐transform infrared (FTIR) spectroscopy. Batch mode experiments were conducted to study the effects of pH, particle size, adsorbent dosage, and sorption time on the adsorptive potential of the prepared activated carbon. Response surface methodology was employed to study the interactions among the variables and to optimize the process conditions for the maximum removal of phosphorus using the coconut shell–based activated carbon (CNS). The characterization results from the FTIR showed the presence of variety of functional groups, such as ?OH, ?NH, C=O, C?H, C?N, CH₃, and CH₂, which explains the CNS's improved adsorption behavior on the colloidal particles. A maximum performance of 95.22% was obtained for CNS at the optimum conditions of adsorbent dosage = 1,000 milligrams (local variable), pH 2 (local variable), particle size = 0.2 millimeters (local variable), and sorption time = 4.2 hours (global variable).     

Derivation of correlations to evaluate the impact of retrofitted post-combustion CO2 capture processes on steam power plant performance

When integrating a post-combustion CO₂ capture process and CO₂ compression into a steam power plant, the three interface quantities heat, electricity and cooling duty must be satisfied by the power plant, leading to a loss in net efficiency. The heat duty shows to be the largest contributor to the overall net efficiency penalty of the power plant. Additional energy penalty results from the cooling and electric power duty of the capture and compression units.In this work, the dependency of the energy penalty on the quantity and quality of the heat duty is analyzed and quantified for a state-of-the-art hard coal fired power plant. Furthermore, the energy penalty attributed to the additional cooling and power duty is quantified. As a result correlations are provided which enable to predict the impact of the heat, cooling and electricity duty of post-combustion CO₂ capture processes on the net output of a steam power plant in a holistic approach.     

Investigations on CO2 storage capacity in saline aquifers: Part 1. Dimensional analysis of flow processes and reservoir characteristics

The CO₂ storage capacity of geological reservoirs is of great interest for the selection of potential storage sites in carbon capture and storage (CCS) projects. A detailed analysis essentially requires a thorough understanding of the interaction of forces acting within the system. By defining characteristic quantities for length, time, pressure and velocity, the governing multiphase flow equations can be non-dimensionalised. This allows for the definition of physically sound dimensionless numbers, resembling the ratios of acting forces like viscous, capillary and gravitational forces. An analysis of the relation of forces in reservoirs with different parameter setups allows their intercomparison with respect to their CO₂ storage capacity potential. To back up the analysis, a comprehensive reservoir parameter database with more than 1200 reservoirs is analysed and statistical characteristics are derived. Effects of reservoir parameters like depth, temperature, absolute and relative permeability, as well as capillary pressure are investigated. It is shown that dimensionless numbers can be used to qualitatively order reservoirs with respect to the forces acting in the reservoir. Moreover, it is shown that the relative permeability relations together with the residual saturations have a great influence on the balance of forces.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

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.     

Site selection in CO2 ocean sequestration: Dependence of CO2 injection rate on eddy activity distribution

Site selection in CO₂ ocean sequestration is examined based on the idea that a site where injected CO₂ is efficiently diluted is favourable in reducing/avoiding biological impacts. Simulations of CO₂ injection into several sites by an eddy-resolving oceanic general circulation model (OGCM) show that the maximum CO₂ concentration differs by a factor of 10 among sites. The distribution of eddy activity is the most important causative factor producing the geographical differences in CO₂ dilution. Based on the relationship between the maximum CO₂ concentration and eddy activity, we estimated the distribution of the maximum CO₂ injection rate by a proposed method, which does not cause chronic impacts on biota. Around Japan, extensive ocean volume has the potential to dilute 20 million tonnes per year without chronic impacts, and some areas can be injected with 80 million tonnes per year.