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.     

Thermodynamic performance of O2/CO2 gas turbine cycle with chemical recuperation by CO2-reforming of methane

This paper proposes a novel power cycle system composed of chemical recuperative cycle with CO₂–NG (natural gas) reforming and an ammonia absorption refrigeration cycle. In which, the heat is recovered from the turbine exhaust to drive CO₂–NG reformer firstly, and then lower temperature heat from the turbine exhaust is provided with the ammonia absorption refrigeration system to generate chilled media, which is used to cool the turbine inlet gas except export. In this paper, a detailed thermodynamic analysis is carried out to reveal the performance of the proposed cycle and the influence of key parameters on performance is discussed. Based on 1 kg s⁻¹ of methane feedstock and the turbine inlet temperature of 1573 K, the simulation results shown that the optimized net power generation efficiency of the cycle rises up to 49.6% on the low-heating value and the exergy efficiency 47.9%, the new cycle system reached the net electric-power production 24.799 MW, the export chilled load 0.609 MW and 2.743 kg s⁻¹ liquid CO₂ was captured, achieved the goal of CO₂ and NO_x zero-emission.     

Properties of char particles obtained under O2/N2 and O2/CO2 combustion environments

Pulverized coal combustion in O₂/N₂ and O₂/CO₂ environments was investigated with a drop tube furnace. Results present that the reaction rate and burn-out degree of O₂/CO₂ chars (obtained in O₂/CO₂ environments) are lower than that of O₂/N₂ chars (obtained in O₂/N₂ environments) under the same experimental condition. It indicates that a higher O₂ concentration in O₂/CO₂ environment is needed to achieve the similar combustion characteristic to that in O₂/N₂ environment. The main differences between O₂/N₂ and O₂/CO₂ chars rely on the pore structure determined by N₂ adsorption and chemical structure measured by FT-IR. For O₂/CO₂ char, the surface is thick and the pores are compact which contribute to the fragmentation reduction of particles burning in O₂/CO₂ environment. The organic functional group elimination rate from the surface of O₂/CO₂ chars is slower or delayed. The present research results might have important implications for further understanding the intrinsic kinetics of pulverized coal combustion in O₂/CO₂ environment.     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

Vesicle formation of polystyrene-block-poly (ethylene oxide) block copolymers induced by supercritical CO2 treatment

A novel route for a preparation of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer vesicles induced by supercritical carbon dioxide (scCO₂) is demonstrated. When PS-b-PEO block copolymer solutions in tetrahydrofuran (THF) are treated with scCO₂ at 70 °C for different times, PS-b-PEO copolymers first assemble into aggregated spheres; then aggregated spheres change into large compound micelles and finally evolve into vesicles. The possible formation mechanism of the vesicles is discussed.     

Simultaneous easy CO2 recovery and drastic reduction of SOx and NOx in O2/CO2 coal combustion with heat recirculation

Coal combustion with O₂/CO₂ is promising because of its easy CO₂ recovery, extremely low NO_x emission and high desulfurization efficiency. Based on our own fundamental experimental data combined with a sophisticated data analysis, its characteristics were investigated. It was revealed that the conversion ratio from fuel-N to exhausted NO in O₂/CO₂ pulverized coal combustion was only about one fourth of conventional pulverized coal combustion. To decrease exhausted NO further and realize simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x, a new scheme, i.e. O₂/CO₂ coal combustion with heat recirculation, was proposed. It was clarified that in O₂/CO₂ coal combustion, with about 40% of heat recirculation, the same coal combustion intensity as that of coal combustion in air could be realized even at an O₂ concentration of as low as 15%. Thus exhausted NO could be decreased further into only one seventh of conventional coal combustion. Simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x could be realized with this new scheme.     

CO2 sorption and transport behavior of ODPA-based polyetherimide polymer films

Plasticization phenomena can significantly reduce the performance of polymeric membranes in high-pressure applications. Polyetherimides (PEIs) are a promising group of membrane materials that combine relatively high CO₂/CH₄ selectivities with high chemical and thermal stability. In this work sorption, swelling, and mixed gas separation performance of 3,3′,4,4′-oxydiphthalic dianhydride (ODPA)-based PEI polymers, with 1, 2 or 3 para-aryloxy substitutions in the diamine moeiety, is investigated under conditions where commercial membranes suffer from plasticization. Particular focus is on the influence of the amount of para-aryloxy substitutions and the film thickness. Results are compared with those of commercially available polymeric membrane materials (sulphonated PEEK, a segmented block-co-polymer PEBAX and the polyimide Matrimid).The glassy polymers display increasing CO₂ sorption with increasing T_g. The larger extent of sorption results from a larger non-equilibrium excess free volume. Swelling of the polymers is induced by sorption of CO₂ molecules in the non-equilibrium free volume as well as from molecules dissolved in the matrix. Dilation of the polymer is similar for each molecule sorbed. Correspondingly, the partial molar volume of CO₂ is similar for molecules present in both regions.Mixed gas separation experiments with a 50/50% CO₂/CH₄ feed gas mixture showed high CO₂/CH₄ selectivities for the ODPA PEI films at elevated pressure. This shows that these materials could potentially be interesting for high-pressure gas separation applications, although additional gas permeation experiments using different feed gas compositions and thin films are required.     

Poly(ethylene terephthalate) nanofibers prepared by CO2 laser supersonic drawing

Poly(ethylene terephthalate) (PET) nanofibers were prepared by irradiating a PET fiber with radiation from a carbon dioxide (CO₂) laser while drawing it at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through the fiber injection orifice. The flow velocity from the orifice was estimated by computer simulation; the fastest flow velocity was calculated to be 401 m s⁻¹ at a chamber pressure of 6 kPa. A nanofiber obtained using a laser power of 8 W and a chamber pressure of 6 kPa had an average diameter of 193 nm and a draw ratio of about 900,000. This technique is a novel method for producing nanofibers.     

Study on coal chars combustion under O2/CO2 atmosphere with fractal random pore model

When predicting the variation of pore structure during O₂/CO₂ combustion of coal chars using the random pore model (RPM), it is impossible to calculate exactly the structure parameter ψ from the pore characteristics. The values of structure parameter ψ, which were calculated based on its fractal feature at various carbon conversions, should be almost constant. However, this investigation exhibited a drastic increase of ψ at the end of combustion reaction. In this work, structure parameter ψ of the RPM was modified according to the experimental analysis and a new model, fractal random pore model (FRPM), was constructed. Compared with other models such as RPM, discrete random pore model (DRPM), the Struis model (Model I) and the Liu model (Model II), it was found that fractal random pore model was more accurate to describe coal chars combustion, especially at higher conversions. Using the FRPM, O₂/CO₂ isotherm combustion of coal chars were analyzed at different temperatures.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.     

A rate equation for Ca(OH)2 and CO2 reaction in a spouted bed reactor at low gas concentrations

In the present study, the carbonation reaction of hydrated lime in semi-dry condition is investigated experimentally in a laboratory-scale spouted bed reactor. Results show that for operating conditions where the concentration of CO₂ is low, the capture efficiency is raised by increasing the inlet CO₂ concentration. Additionally, because of the inconsistency between the experimental reaction rate and the calculated values based on the previous proposed equations, a new rate equation is introduced that considers the dependency of CO₂ concentration too. To validate the proposed equation, its predictions were compared with another set of experimental data.     

CO2 capture by adsorption with nitrogen enriched carbons

The success of CO₂ capture with solid sorbents is dependent on the development of a low cost sorbent with high CO₂ selectivity and adsorption capacity. Immobilised amines are expected to offer the benefits of liquid amines in the typical absorption process, with the added advantages that solids are easy to handle and that they do not give rise to corrosion problems. In this work, different alkylamines were evaluated as a potential source of basic sites for CO₂ capture, and a commercial activated carbon was used as a preliminary support in order to study the effect of the impregnation. The amine coating increased the basicity and nitrogen content of the carbon. However, it drastically reduced the microporous volume of the activated carbon, which is chiefly responsible for CO₂ physisorption, thus decreasing the capacity of raw carbon at room temperature.     

Production of bioethanol under high pressure of CO2: The effect of process conditions

The aim of this work is to investigate the possibility of producing ethanol by glucose fermentation under high pressure of carbon dioxide up to 48 bar, in order to exploit both ethanol and denser CO₂ as a by-product of the process. The fermentation is carried out using Ethanol Red™-Lesaffre Saccharomyces cerevisiae yeast strain, which is commonly applied in industrial bioethanol production.The experiments were performed in six small reactors (2 mL of volume each) connected in parallel, to investigate the effect of the process variables at the same conditions of temperature and pressure, and in one pilot reactor (1 L of volume) to confirm the results obtained at the lower scale.The influence of operative variables, such as carbon dioxide pressure (0–48 bar), temperature (32 and 36 °C), glucose (150–250 g/L), inositol (0–400 mg/L) and biomass concentration (OD 2 and 3.5), was measured in terms of ethanol concentration (by gas chromatography) and ethanol productivity (expressed as grams of ethanol per CFU of yeast). Both of these parameters were found to be strongly dependent on glucose concentration and CO₂ pressure, which negatively affects the fermentation. Nevertheless, also at 50 bar it is possible to produce appreciable amounts of ethanol.     

Preparation of ceramic nanospheres by CO2 laser vaporization (LAVA)

In order to prepare ceramic nanoparticles by CO₂ laser vaporization (LAVA) coarse ceramic powders (e.g. ZrO₂, Al₂O₃, and TiO₂) were used as raw materials. The raw powder was vaporized into a flowing process gas under normal pressure. Expanding into the gas, the vapor instantly cools down. Gas-phase condensation leads to the formation of nanoscale particles with a composition that corresponds to that of the raw powder. LAVA nanoparticles are chemically pure, spherical, crystalline, exhibit a narrow size distribution, and form merely soft agglomerates. The co-laser vaporization of mixtures of ceramic raw powders allows for the preparation of nanoparticles of multi-phase (e.g. Fe₂O₃-SiO₂) or single-phase (e.g. CaTiO₃) mixed-oxides and dispersion ceramics (e.g. ZrO₂-Al₂O₃). In order to modify the surface of the nanoparticles they can be coated in-process with an organic additive. Thus, the LAVA method allows for the targeted development of a wide range of ceramic nanopowders with tailored properties.     

Photoinduced activation of CO2 on TiO2 surfaces: Quantum chemical modeling of CO2 adsorption on oxygen vacancies

Chemical processes that utilize CO₂ emissions from coal-fired power plants will be required as the world progresses towards reducing CO₂ emissions. The conversion of CO₂ using light energy (CO₂ photoreduction) has the potential to produce useful fuels or valuable chemicals while decreasing CO₂ emissions from the use of fossil fuels such as coal. Computational studies on the initial steps of photoinduced CO₂ activation on TiO₂ surfaces, necessary to develop a mechanistic understanding of CO₂ photoreduction are a focus of this article.The results from previous quantum mechanical modeling studies conducted by the authors indicated that stoichiometric TiO₂ surfaces likely do not promote electron transfer to CO₂. Therefore, the role of oxygen vacancies in promoting the light-induced conversion of CO₂ (CO₂ photoreduction) on TiO₂ surfaces was examined in this study. Two different side-on bonded bent-CO₂ (bridging Ti-CO₂^δ•−-Ti species) were formed on the reduced rutile (110) and anatase (010), (001) surfaces, indicating charge transfer from the reduced surface to CO₂. Further steps in the photoexcitation of these bent-CO₂ species were investigated with density functional theory calculations. Consistent with CO₂ adsorption and photodesorption on other n-type metal oxides such as ZrO₂, the results suggest that the bent-CO₂ species do not gain further charge from the TiO₂ surface under illumination and are likely photodesorbed as neutral species. Additionally, although the formation of species such as CO and HCHO is thermodynamically possible, the energy needed to regenerate the oxygen vacancy on TiO₂ surfaces (~ 7 eV) is greater than that available through band-gap illumination (3.2 eV). Therefore, CO₂ reactions with water on irradiated anatase TiO₂ surfaces are likely to be stoichiometric.     

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.     

Experimental study of ash formation during pulverized coal combustion in O2/CO2 mixtures

The present paper was addressed to mineral transformations and ash formation during O₂/CO₂ combustion of pulverized coal. Four Chinese thermal coals were burned in a drop tube furnace to generate ashes under various combustion conditions. The ash samples were characterized with XRD analysis and ⁵⁷Fe Mössbauer spectroscopy. The impacts of O₂/CO₂ combustion on mineral transformation and ash formation were explored through comparisons between O₂/CO₂ combustion and O₂/N₂ combustion. It was found that, O₂/CO₂ combustion did not significantly change the mineral phases formed in the residue ashes, but did affect the relative amounts of the mineral phases. The differences observed in the ashes formed in two atmospheres were attributed to the impact of the gas atmosphere on the combustion temperatures of coal char particles, which consequently influenced the ash formation behaviors of included minerals.