Thermodynamics and regeneration of CO2 adsorption on mesoporous spherical-silica particles

Mesoporous spherical-silica particles (MSPs) were modified by N-[3-(trimethoxysilyl) propyl]ethylenediamine (EDA) solution and were employed as sorbents to study thermodynamics and regeneration of CO₂ adsorption from gas streams. The thermodynamic analysis gave low isosteric heats of adsorption, which are typical for physical adsorption. The cyclic CO₂ adsorption on MSP(EDA) showed that the adsorbed CO₂ could be effectively desorbed via thermal treatment at 120 °C for 25 min while the adsorbed CO₂ due to physical interaction could be effectively desorbed via vacuum suction at 0.145 bar for 30 min. If a combination of thermal treatment and vacuum suction was conducted at 120 °C and 0.145 bar, the time for effectively desorbing CO₂ could be shortened to 7.5 min and thus reduces a significant amount of energy penalty. The adsorption capacities and the physicochemical properties of MSP(EDA) were preserved after 15 cycles of adsorption and regeneration. These results suggest that the MSP(EDA) can be stably employed in the prolonged cyclic adsorption and that they are thus possibly cost-effective sorbents for CO₂ capture from flue gases.     

Reduction of amine mist emissions from a pilot-scale CO2 capture process using charged colloidal gas aphrons

In the CO₂ capture process from coal-derived flue gas where amine solvents are used, the flue gas can entrain small liquid droplets into the gas stream leading to emission of the amine solvent. The entrained drops, or mist, will lead to high solvent losses and cause decreased CO₂ capture performance. In order to reduce the emissions of the fine amine droplets from CO₂ absorber, a novel method using charged colloidal gas aphron (CGA) generated by an anionic surfactant was developed. The CGA absorption process for MEA emission reduction was optimized by investigating the surfactant concentration, stirring speed of the CGA generator, and capture temperature. The results show a significant reduction of MEA emissions of over 50% in the flue gas stream exiting the absorber column of a pilot scale CO₂ capture unit.     

A Single Stage Membrane Process for CO2 Capture from Flue Gas by a Facilitated Transport Membrane

Carbon dioxide is the most important anthropogenic greenhouse gas and it accounts for about 80% of all greenhouse gases (GHG). The global atmospheric CO₂ concentrations have been increased significantly and have become the major source responsible for global warming; the greatest environmental challenge the world is facing now. The efforts to control the GHG emissions include the recovery of CO₂ from flue gas. In this work, feasibility analysis, based on a single stage membrane process, has been carried out with an in-house membrane program interfaced within process simulation program (AspenHysys) to investigate the influence of process parameters on the energy demand and flue gas processing cost. A novel CO₂-selective membrane with the facilitated transport mechanism has been employed to capture CO₂ from the flue gas mixtures. The results show that a membrane process using the facilitated transport membrane can also be considered as an alternative CO₂ capture process and it is possible to achieve more than 90% CO₂ recovery and 90% CO₂ purity in the permeate with reasonable energy consumption compared to amine absorption and other capture techniques.     

Theoretical and experimental study on the emission characteristics of waste plastics incineration by modified O2/RFG combustion technology

For mitigating the emission of greenhouse gas CO₂ from general air combustion systems, a clean combustion technology O₂/RFG is in development. The O₂/RFG combustion technology can significantly enhance the CO₂ concentration in the flue gas; however, using almost pure oxygen or pure CO₂ as feed gas is uneconomic and impractical. As a result, this study proposes a modified O₂/RFG combustion technology in which the minimum pure oxygen is mixed with the recycled flue gas and air to serve as the feed gas. The effects of different feed gas compositions and ratios of recycled flue gas on the emission characteristics of CO₂, CO and NO_x during the plastics incineration are investigated by theoretical and experimental approaches.Theoretical calculations were carried out by a thermodynamic equilibrium program and the results indicated that the emissions of CO₂ were increased with the O₂ concentrations in the feed gas and the ratios of recycled flue gas increased. Experimental results did not have the same trends with theoretical calculations. The best feed gas composition of the modified O₂/RFG combustion was 40% O₂ + 60% N₂ and the best ratio of recycled flue gas was 15%. As the O₂ concentration in feed gas and the ratio of recycled flue gas increased, the total flow rates and pressures of feed gas reduced. The mixing of solid waste and feed gas was incomplete and the formation of CO₂ decreased. Moreover, the emission of CO was decreased as the O₂ concentration in feed gas and the ratio of recycled flue gas increased. The emission of NO_x gradually increased with rising the ratio of recycled flue gas at lower O₂ concentration (<40%) but decreased at higher O₂ concentration (>60%).     

CO2 capture using some fly ash-derived carbon materials

Adsorption is considered to be one of the more promising technologies for capturing CO₂ from flue gases. For post-combustion capture, the success of such an approach is however dependent on the development of an adsorbent that can operate competitively at relatively high temperatures. In this work, low cost carbon materials derived from fly ash, are presented as effective CO₂ sorbents through impregnation these with organic bases, for example, polyethylenimine aided by polyethylene glycol. The results show that for samples derived from a fly ash carbon concentrate, the CO₂ adsorption capacities were relatively high (up to 4.5 wt%) especially at high temperatures (75 °C), where commercial active carbons relying on physi-sorption have low capacities. The addition of PEG improves the adsorption capacity and reduces the time taken for the sample to reach the equilibrium. No CO₂ seems to remain after desorption, suggesting that the process is fully reversible.     

CO2 capture using oxygen enhanced combustion strategies for natural gas power plants

This paper describes a series of experiments conducted with natural gas in air and in mixtures of oxygen and recycled flue gas, termed O₂/CO₂ recycle combustion. The objective is to enrich the flue gas with CO₂ to facilitate its capture and sequestration. Detailed measurements of gas composition, flame temperature and heat flux profiles were taken inside CANMET's 0.3 MWth down-fired vertical combustor fitted with a proprietary pilot scale burner. Flue gas composition was continuously monitored. The effects of burner operation, including swirling of secondary stream and air staging, on flame characteristics and NO_x emissions were also studied. The results of this work indicate that oxy-gas combustion techniques based on O₂/CO₂ combustion with flue gas recycle offer excellent potential for retrofit to conventional boilers for CO₂ emission abatement. Other benefits of the technology include considerable reduction and even elimination of NO_x emissions, improved plant efficiency due to lower gas volume and better operational flexibility.     

Modelling of a fluidized bed carbonator reactor to capture CO2 from a combustion flue gas

In recent years several processes incorporating a carbonation-calcination loop in an interconnected fluidized bed reactor have been proposed as a way to capture CO₂ from flue gases. This paper is a first approximation to the modelling of a fluidized bed carbonator reactor. In this reactor the flue gas comes into contact with an active bed composed of particles with very different activities, depending on their residence time in the bed and in the carbonation-calcination loop. The model combines the residence time distribution functions with existing knowledge about sorbent deactivation rates and sorbent reactivity. The fluid dynamics of the solids (CSTR) and gases (PF) in the carbonator are based on simple assumptions. The carbonation rates are modelled defining a characteristic time for the transition between a fast reaction regime to a regime with a zero reaction rate. On the basis of these assumptions the model is able to predict the CO₂ capture efficiency for the flue gas depending on the operating and design conditions. Operating windows with high capture efficiencies are discussed, as well as those conditions where only modest capture efficiencies are possible.     

Investigation into a gas–solid–solid three-phase fluidized-bed carbonator to capture CO2 from combustion flue gas

A two-dimensional (2D) transient model was developed to simulate the local hydrodynamics of a gas (flue gas)–solid (CaO)–solid (CaCO₃) three-phase fluidized-bed carbonator using the computational fluid dynamic method, where the chemical reaction model was adopted to determine the molar fraction of CO₂ at the exit of carbonator and the partial pressure of CO₂ in the carbonator. This investigation was intended to improve an understanding of the chemical reaction effects of CaO with CO₂ on the CO₂ capture efficiency of combustion flue gases. For this purpose, we had utilized Fluent 6.2 to predict the CO₂ capture efficiency for different operation conditions. The adopted model concerning the reaction rate of CaO with CO₂ is joined into the CFD software. Model simulation results, such as the local time-averaged CO₂ molar fraction and conversion of CaO, were validated by experimental measurements under varied operating conditions, e.g., the fraction of active CaO, chemical reaction temperature, particle size, and cycle number at different locations in a gas–solid–solid three-phase fluidized bed carbonator. Furthermore, the local transient hydrodynamic characteristics, such as gas molar fraction and partial pressure were predicted reasonably by the chemical reaction model adopted for the dynamic behaviors of the gas–solid–solid three-phase fluidized bed carbonator. On the basis of this analysis, capture CO₂ strategies to reduce CO₂ molar fraction in exit of carbonator reactor can be developed in the future. It is concluded that a fluidized bed of CaO can be a suitable reactor to achieve very effective CO₂ capture from combustion flue gases.     

Results from trialling aqueous NH3 based post-combustion capture in a pilot plant at Munmorah power station: Absorption

Australia's Commonwealth Scientific and Industrial Research Organization (CSIRO) and Delta Electricity have developed, commissioned and operated an A$7 million aqueous NH₃ based post-combustion capture (PCC) pilot plant at the Munmorah black coal fired power station in Australia. The results from the pilot plant trials will be used to address the gap in know-how on application of aqueous NH₃ for post-combustion capture of CO₂ and other pollutants in the flue gas and explore the potential of the NH₃ process for application in the Australia power sector. This paper is one of a series of publications to report and discuss the experimental results obtained from the pilot plant trials and primarily focuses on the absorption section.The pilot plant trials have confirmed the technical feasibility of the NH₃ based capture process. CO₂ removal efficiency of more than 85% can be achieved even with low NH₃ content of up to 6 wt%. The NH₃ process is effective for SO₂ but not for NO in the flue gas. More than 95% of SO₂ in the flue gas is removed in the pre-treatment column using NH₃. The mass transfer coefficients for CO₂ in the absorber as functions of CO₂ loading and NH₃ concentration have been obtained based on pilot plant data.     

Comparison of solvent performance for CO2 capture from coal-derived flue gas: A pilot scale study

The performance of a proprietary solvent (CAER-B2), an amine-carbonate blend, for the absorption of CO₂ from coal-derived flue gas is evaluated and compared with state-of-the-art 30 wt% monoethanolamine (MEA) under similar experimental conditions in a 0.1 MWth pilot plant. The evaluation was done by comparing the carbon capture efficiency, the overall mass transfer rates, and the energy of regeneration of the solvents. For similar carbon loadings of the solvents in the scrubber, comparable mass transfer rates were obtained. The rich loading obtained for the blend was 0.50 mol CO₂/mol amine compared to 0.44 mol CO₂/mol amine for MEA. The energy of regeneration for the blend was about 10% lower than that of 30 wt% MEA. At optimum conditions, the blend shows promise in reducing the energy penalty associated with using industry standard, MEA, as a solvent for CO₂ capture.     

Microporous phenol-formaldehyde resin-based adsorbents for pre-combustion CO2 capture

Different types of phenolic resins were used as precursor materials to prepare adsorbents for the separation of CO₂ in pre-combustion processes. In order to obtain highly microporous carbons with suitable characteristics for the separation of CO₂ and H₂ under high pressure conditions, phenol-formaldehyde resins were synthesised under different conditions. Resol resins were obtained by using an alkaline environment while Novolac resins were synthesised in the presence of acid catalysts. In addition, two organic additives, ethylene glycol (E) and polyethylene glycol (PE) were included in the synthesis. The phenolic resins thus prepared were carbonised at different temperatures and then physically activated with CO₂. The carbons produced were characterised in terms of texture, chemical composition and surface chemistry. Maximum CO₂ adsorption capacities at atmospheric pressure were determined in a thermogravimetric analyser. Values of up to 10.8 wt.% were achieved. The high-pressure adsorption of CO₂ at room temperature was determined in a high-pressure magnetic suspension balance. The carbons tested showed enhanced CO₂ uptakes at high pressures (up to 44.7 wt.% at 25 bar). In addition, it was confirmed that capture capacities depend highly on the microporosity of the samples, the narrow micropores (pore widths of less than 0.7 nm) being the most active in CO₂ adsorption at atmospheric pressure. The results presented in this work suggest that phenol-formaldehyde resin-derived activated carbons, particularly those prepared with the addition of ethylene glycol, show great potential as adsorbents for pre-combustion CO₂ capture.     

Dynamics of CO2 adsorption on sodium oxide promoted alumina in a packed-bed reactor

CO₂ adsorption in packed-bed reactors has potential applications in flue gas CO₂ capture and adsorption enhanced reaction processes. This work focuses on CO₂ adsorption dynamics on sodium oxide promoted alumina in a packed-bed reactor. A comprehensive model is developed to describe the coupled transport phenomena and is solved using orthogonal collocation on finite elements. The model predicted breakthrough curve matches very well with experimental data obtained from a pilot-scale packed-bed reactor. Several dimensionless parameters are also derived to explain the shape of the breakthrough curve.     

Pilot plant study of two new solvents for post combustion carbon dioxide capture by reactive absorption and comparison to monoethanolamine

Application of new solvents will substantially contribute to the reduction of the energy demand for the post combustion capture of CO₂ from power plant flue gases. The present work describes tests of such new solvents in a gas-fired pilot plant, which comprises the complete absorption/desorption process (column diameters 0.125 m, absorber/desorber packing height 4.25/2.55 m, packing type: Sulzer BX 500, flue gas flow 30–100 kg/h, CO₂ partial pressure 35–135 mbar). Two new solvents CESAR1 (0.28 g/g 2-amino-2-methyl-1-propanol+0.17 g/g piperazine+0.55 g/g H₂O) and CESAR2 (0.32 g/g 1, 2-ethanediamine+0.68 g/g H₂O), which were developed in an EU-project, were systematically studied and compared to MEA (0.3 g/g monoethanolamine+0.7 g/g H₂O). The two new solvents and MEA were studied in the same way in the pilot plant and detailed results are reported for all solvents. In the present study the structured packing Sulzer BX 500 is used. The measurements are carried out at a constant CO₂ removal rate of 90% by an adjustment of the regeneration energy in the desorber for systematically varied solvent flow rates. An optimal solvent flow rate leading to a minimum energy requirement is found from these studies. Direct comparisons of such results can be misleading if there are differences in the kinetics of the different solvent systems. The influence of kinetic effects is experimentally studied by varying the flue gas flow rate at a constant ratio of solvent mass flow to flue gas mass flow and constant CO₂ removal rate. Results from these studies indicate similar kinetics for CESAR1, CESAR2 and MEA. The direct comparison of the pilot plant results for these solvents is therefore justified. Both CESAR1 and CESAR2 show improvements compared to MEA. The most promising is CESAR1 with a reduction of about 20% in the regeneration energy and 45% in the solvent flow rate.     

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

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

Combustion characteristics of coal in a mixture of oxygen and recycled flue gas

The combustion of coal in a mixture of pure O₂ and recycled flue gas is one variant of a novel combustion approach called oxy-fuel combustion. With the absence of N₂, this approach leads to a flue gas stream highly enriched in CO₂. For many applications, this flue gas stream can then be compressed and sequestered without further separation. As a result, oxy-fuel combustion is an attractive way to capture CO₂ produced from fossil fuel combustion. When coal is burned in this O₂ and CO₂ rich environment, its combustion characteristics can be very different from conventional air-fired combustion. In CETC-O, a vertical combustor research facility has been used in the past years to investigate the combustion characteristics of several different coals with this variant of oxy-fuel combustion. This included flame stability, emissions of NO_x, SO_x and trace elements, heat transfer, in-furnace flame profiles and flue gas compositions. This paper will report some of the major findings obtained from these research activities.     

Effect of water pretreatment on CO<Subscript>2</Subscript> capture using a potassium-based solid sorbent in a bubbling fluidized bed reactor

A bubbling fluidized bed reactor was used to study CO₂ capture from flue gas by using a potassium-based solid sorbent, sorbKX35 which was manufactured by the Korea Electric Power Research Institute. A dry sorbent, sorbKX35, consists of K₂CO₃ for absorption and supporters for mechanical strength. To increase initial CO₂ removal, some amount of H₂O was absorbed in the sorbent before injecting simulated flue gas. It was possible to achieve 100% CO₂ removal for more than 10 minutes at 60°C and a residence time of 2 s with H₂O pretreatment. When H₂O pretreatment time was long enough to convert K₂CO₃ of sorbKX35 into K₂CO₃ · 1.5H₂O, CO₂ removal was excellent. The results obtained in this study can be used as basic data for designing and operating a large scale CO₂ capture process with two fluidized bed reactors. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Carbon dioxide absorption into biphasic amine solvent with solvent loss reduction

The main challenge in the CO₂ capture from flue gases is to reduce the energy consumption required for solvent regeneration. Lipophilic amines exhibit a thermomorphic phase transition upon heating, giving rise to autoextractive behaviour, which enhances desorption at temperatures well below the solvent boiling point. The low regeneration temperature of less than 80 °C together with the high cyclic CO₂ loading capacity (c. 0.9 mol-CO₂/mol-absorbent) of such biphasic amine systems permit the use of low temperature and even waste heat for desorption purposes. In order to improve the capture process and reduce the commensurate energy demand still further, desorption experiments were carried out at 70-80 °C and techniques for enhancing CO₂ release without gas stripping were also studied. The comparison of various amines at a concentration of 3 M and for a 15 mol% CO₂ feed gas demonstrates the considerable potential of lipophilic amines for the CO₂ absorption process. Chemical stability is a decisive factor for the industrial application of amine absorbents. Degradation of the novel lipophilic amine absorbents was shown to be minor, while volatility losses represent a major shortcoming of the biphasic solvent systems. Appropriate countermeasures to limit solvent losses were examined experimentally.     

Efficient capture of CO2 from flue gas at high temperature by tunable polyamine-based hybrid ionic liquids

For an ideal absorbent for CO₂ capture from flue gas, there are some key features including easy preparation, high stability, low absorption enthalpy, high capacity at high temperature and excellent reversibility. Herein, several polyamine-functionalized ionic liquids (ILs) were easily prepared from cheap polyamines and lithium salts, which exhibited significantly improved stability due to the presence of multisite coordinating interactions. The viscosity was reduced by introducing polyalcohol-based ILs, leading to polyamine-based hybrid ILs. Interestingly, these polyamine-based hybrid ILs exhibited high CO₂ capacity (4.09 mmol/g, 0.1 bar) at high temperature (80°C) and excellent reversibility in the presence of H₂O and O₂, which is superior to many other good absorbents. Moreover, these ILs also showed good performance for CO₂ capture from stimulated air (2.10 mmol/g, 380 ppm). We believe that this method with easy preparation, low cost, high efficiency and excellent reversibility has a great potential in the industrial capture of CO₂ from flue gas.     

Preliminary analysis of process flow sheet modifications for energy efficient CO2 capture from flue gases using chemical absorption

The energy penalty associated with solvent based capture of CO₂ from power station flue gases can be reduced by incorporating process flow sheet modifications into the standard process. A review of modifications suggested in the open and patent literature identified several options, primarily intended for use in the gas processing industry. It was not immediately clear whether these options would have the same benefits when applied to CO₂ capture from near atmospheric pressure combustion flue gases. Process flow sheet modifications, including split flow, rich split, vapour recompression, and inter-stage cooling, were therefore modelled using a commercial rate-based simulation package. The models were completed for a Queensland (Australia) based pilot plant running on 30% MEA as the solvent. The preliminary modelling results showed considerable benefits in reducing the energy penalty of capturing CO₂ from combustion flue gases. Further work will focus on optimising and validating the most relevant process flow sheet modifications in a pilot plant.     

Partial O2-fired coal power plant with post-combustion CO2 capture: A retrofitting option for CO2 capture ready plants

In the work presented in this paper, an alternative process concept that can be applied as retrofitting option in coal-fired power plants for CO₂ capture is examined. The proposed concept is based on the combination of two fundamental CO₂ capture technologies, the partial oxyfuel mode in the furnace and the post-combustion solvent scrubbing. A 330 MW_el Greek lignite-fired power plant and a typical 600 MW_el hard coal plant have been examined for the process simulations. In a retrofit application of the ECO-Scrub technology, the existing power plant modifications are dominated by techno-economic restrictions regarding the boiler and the steam turbine islands. Heat integration from processes (air separation, CO₂ compression and purification and the flue gas treatment) can result in reduced energy and efficiency penalties. In the context of this work, heat integration options are illustrated and main results from thermodynamic simulations dealing with the most important features of the power plant with CO₂ capture are presented for both reference and retrofit case, providing a comparative view on the power plant net efficiency and energy consumptions for CO₂ capture. The operational characteristics as well as the main figures and diagrams of the plant’s heat balances are included.