An investigation into the likely impact of oxy-coal retrofit on fire-side corrosion behavior in utility boilers

Real-time electrochemical measurements of corrosion rate were performed to evaluate the respective corrosion rates of one boiler waterwall material (SA210) and three boiler superheater materials (T22, P91 and 347H) while firing Utah Western bituminous, Illinois high-sulfur bituminous and Powder River Basin (PRB) sub-bituminous coals in a 1.5 MW pulverized coal-fired furnace. The raw average measured corrosion rates were very low, between 0.0003 and 0.016 mm/year (0.012 and 0.63 mils/year) for most materials under air- and oxy-fired conditions. For some high-sulfur conditions measured corrosion rates were as high as 0.72 mm/year (28 mils/year). Waterwall corrosion rates decreased consistently when converting from air- to oxy-firing while superheater corrosion rates generally increased, although they were less than twice the air-fired rate under most conditions. Corrosion rates for the lower alloyed materials (SA210 and T22) increased significantly during transients from reducing to oxidizing conditions. Measured increases in the corrosion rate of 347H material under high sulfur and low temperature conditions, and associated decrease in corrosion rate at higher temperatures on this alloy, were consistent with the formation of trisulphates in the superheater deposits. The increase of corrosion rate with increased metal temperatures was demonstrated, as was the consistently repeatable nature of the observed results.     

Ash and deposit formation from oxy-coal combustion in a 100 kW test furnace

Ash deposition is still an unresolved problem when retrofitting existing air-fired coal power plants to oxy-fuel combustion. Experimental data are quite necessary for mechanism validation and model development. This work was designed to obtain laboratory combustor data on ash and deposits from oxy-coal combustion, and to explore the effects of oxy-firing on their formation. Two bituminous coals (Utah coal and Illinois coal) and one sub-bituminous coal (PRB coal) were burned on a down-fired combustor under both oxy- and air-firing. Two oxy-fired cases, i.e., 27 vol% O₂/73 vol% CO₂ and 32 vol% O₂/68 vol% CO₂, were selected to match the radiation flux and the adiabatic flame temperature of air combustion, respectively. Once-through CO₂ was used to simulate fully cleaned recycled flue gas. The flue gas excess oxygen was fixed at 3 vol%. For each case, both size-segregated fly ash and bulk fly ash samples were obtained. Simultaneously, ash deposits were collected on an especially designed un-cooled deposition probe. Ash particle size distributions and chemical composition of all samples were characterized. Data showed that oxy-firing had insignificant impacts on the tri-modal ash particle size distributions and composition size distributions in the size range studied. Bulk ash compositions also showed no significant differences between oxy- and air-firing, except for slightly higher sulfur contents in some oxy-fired ashes. The oxy-fired deposits were thicker than those from air-firing, suggesting enhanced ash deposition rates in oxy-firing. Oxy-firing also had apparent impacts on the deposit composition, especially for those components (e.g., CaO, Fe₂O₃, SO₃, etc.) that could contribute significantly to ash deposition. Based on these results, aerodynamic changes in gas flow and changes in combustion temperature seemed more important than chemical changes of ash particles in determining deposit behavior during oxy-coal combustion.     

Large eddy simulation of oxy-coal combustion in an industrial combustion test facility

Oxy-fuel combustion is considered as one of the most promising technologies for carbon capture and storage (CCS). In this study, a commercial computational fluid dynamics (CFD) code has been employed for the simulation of an air-fired coal combustion and an oxy-fired coal combustion with recycled flue gas in a 1 MW_th combustion test facility. Reynolds–averaged Navier–Stokes (RANS) solutions have been obtained for both cases. Results indicate that the CFD code with existing physical sub-models can provide a reasonable prediction for the air-fired combustion. However, the prediction for the oxy-fired case has not been as satisfactory as expected. In order to assess the impact of the turbulence treatment in CFD on the predictions, large eddy simulation (LES) has been performed for oxy-fired case and compared with the results from the RANS simulation and the available experimental data. Although the results suggest that LES can provide a more realistic prediction of the shape and the physical properties of the flame, there has not been significant improvement in the prediction of the temperature. In addition, the complexity of the problem requires more detailed experimental data for the validation of the LES. In order to improve the validity of numerical simulations for design purposes, further modelling improvements for oxy-coal combustion that are necessary for more accurate predictions are addressed. Based on this study, it is envisaged that the complexity in the oxy-coal combustion process requires more detailed analyses of the available physical sub-models.     

Sulfur trioxide formation during oxy-coal combustion

The purpose of this study was to investigate the effects of increased oxygen and carbon dioxide concentration on the formation of sulfur trioxide during oxy-coal combustion in two different types of pilot-scale furnaces: a pulverized-coal and a circulating-fluidized-bed-fired system.For pulverized-coal (PC) testing, concentrations of SO₃ and SO₂ were significantly higher for oxy-fired conditions as compared to air-fired conditions. For a high-sulfur Illinois bituminous coal, SO₃ concentrations were 4–6 times greater on average. When firing a low-sulfur Utah Bituminous coal, SO₃ concentrations were similar for oxy-firing vs. air-firing, and the overall levels were very low compared to the Illinois coal, consistent with differences in the fuel sulfur contents. PC-fired emissions on a normalized mass basis (mass SO₃ per unit energy input) indicated higher SO₃ emissions under air-fired conditions vs. oxy-firing, for both the Illinois and Utah coals.Circulating fluidized bed testing was also carried out using the low-sulfur Utah coal, and SO₃ concentrations were notably higher for oxy-firing vs. air-firing, in contrast to the similar concentration levels observed for PC-firing. When compared on a normalized mass basis, the emissions were similar for both air- and oxy-firing, which is also in contrast to the PC-fired results for this coal.     

Carbon dioxide capture from combustion flue gases with a calcium oxide chemical loop. Experimental results and process development

Post-combustion carbonate looping processes are based on the capture of carbon dioxide from the flue gases of an existing power plant in a circulating fluidized bed reactor (CFB) of calcium oxide (the carbonator) particles. The calcination of calcium carbonate in a new oxy-fired CFBC power plant regenerates the sorbent (calcium oxide particles) and obtains high purity carbon dioxide. This communication presents experimental results from a small test facility (30 kWt) operated in continuous mode using two interconnected CFB reactors as carbonator and calciner. Capture efficiencies between 70 and 97% have been obtained under realistic flue gas conditions in the carbonator reactor (temperatures around 650 °C). The similarity between process conditions and those existing in CFBC power plants should allow a rapid scaling up of this technology. The next steps for this process development are also outlined.     

Thermal radiation in oxy-fuel flames

This work investigates thermal radiation in oxy-fuel flames, based on experiments and modelling. Experiments were conducted in a 100 kW test facility in air and oxy-fuel combustion atmospheres, using two different types of fuels, lignite and propane. In-flame measurements of gas composition, temperature and total radiation intensity, were performed and used as input to radiation modelling to examine the influence of oxy-fuel conditions on gas and particle radiation characteristics. In the modelling, the spectral properties of CO₂ and H₂O are treated by means of a statistical narrow band model and particle radiation is modelled for both scattering and non-scattering particles.Experiments on the propane flame show that the flame radiation conditions are drastically influenced by the recycling conditions. With OF 27 conditions (27% oxygen in the feed gas) and dry recycling, the temperature is slightly lower compared to air-fired conditions, but the emitted intensity is significantly increased. Modelling shows that this is mainly caused by a significantly increased soot radiation. Propane flame images show that the presence of soot in oxy-fuel conditions varies strongly with recycling conditions. The contribution due to an increased emission by CO₂ is of minor importance. In the lignite experiments similar flame temperatures were kept during air and oxy-fuel combustion (OF 25 conditions with dry recycling). The measurements show that the intensity levels in both flames are similar which is due to a strong particle radiation in both environments. The modelling reveals that the dominance by particle radiation contra gas radiation is closely related to whether the particles are scattering or non-scattering.     

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.     

Development of mixed conducting membranes for clean coal energy delivery

Mixed conducting membranes can be used for the separation of oxygen from air in both coal gasification and oxy-fuel power plants. In this review paper, the basic perovskite and non-perovskite structures, composition, properties and performance are addressed. Two typical perovskite materials, BSCF and LSCF, show promise in industrial applications as their oxygen fluxes are at least one order of magnitude higher than non-perovskite membranes. BSCF membranes are now delivering oxygen fluxes in excess of 5 ml min^?1 cm^?2. Latest developments in perovskite composition, effects of impurities in membrane performance and membrane geometry are discussed giving an insight into the potential utilisation in clean energy delivery processes. Strategies for improving membranes performance using unit operations with different geometries and possible future technologies are also addressed.     

Pulverized coal stream ignition delay under conventional and oxy-fuel combustion conditions

The coal stream ignition process is critical to the performance of modern pulverized coal burners, particularly when operating under novel conditions such as experienced in oxy-fuel combustion. However, experimental studies of coal stream ignition are lacking, and recent modeling efforts have had to rely on comparisons with a single set of experiments in vitiated air. To begin to address this shortfall, we have conducted experiments on the ignition properties of two U.S. and two Chinese coals in a laminar entrained flow reactor. Most of the measurements focused on varying the coal feed rate for furnace temperatures of 1230–1320 K and for 12–20 vol.% O₂ in nitrogen. The influence of coal feed rate on ignition with a carbon dioxide diluent was also measured for 20 vol.% O₂ at 1280 K. A second set of measurements was performed for ignition of a fixed coal feed rate in N₂ and CO₂ environments at identical furnace temperatures of 1200 K, 1340 K, and 1670 K. A scientific CCD camera equipped with a 431 nm imaging filter was used to interrogate the ignition process. Under most conditions, the ignition delay decreased with increasing coal feed rate until a minimum was reached at a feed rate corresponding to a particle number density of approximately 4 × 10⁹ m^?3 in the coal feed pipe. This ignition minimum corresponds to a cold flow group number, G, of ～0.3. At higher coal feed rates the ignition delay increased. The ignition delay time was shown to be very sensitive to (a) the temperature of the hot coflow into which the coal stream is introduced, and (b) the coal particle size. The three high volatile bituminous coals showed nearly identical ignition delay as a function of coal feed rate, whereas the subbituminous coal showed slightly greater apparent ignition delay. Bath gas CO₂ content was found to have a minor impact on ignition delay.     

Validation of spectral gas radiation models under oxyfuel conditions—Part B: Natural gas flame experiments

Combustion of hydrocarbon fuels with pure oxygen results in a different flue gas composition as combustion with air. Standard CFD spectral gas radiation models for air blown combustion are out of their validity range. The series of three articles provides a common spectral basis for the validation of new developed models. Part B of the series presents spectral measurements in the spectral range of 2.4–5.4 μm of a 70 kW turbulent natural gas flame in air blown combustion and in wet and dry oxyfuel combustion. The experimentally measured intensity spectra were compared with simulated spectra based on measured gas atmospheres. The line-by-line database HITEMP2010 and the two statistical-narrow-band models EM2C and RADCAL were used for the numerical simulation. The measured spectra showed large fluctuations due to turbulence. The up to 75% increased averaged experimental intensity compared to the simulated intensity pointed out the importance of the effect of turbulence-radiation-interaction in combustion simulations.     

Carbon dioxide storage capacity in uneconomic coal beds in Alberta,Canada: Methodology,potential and site identification

Methodology is presented for a first-order regional-scale estimation of CO₂ storage capacity in coals under sub-critical conditions, which is subsequently applied to Cretaceous-Tertiary coal beds in Alberta, Canada. Regions suitable for CO₂ storage have been defined on the basis of groundwater depth and CO₂ phase at in situ conditions. The theoretical CO₂ storage capacity was estimated on the basis of CO₂ adsorption isotherms measured on coal samples, and it varies between ∼20 kt CO₂/km² and 1260 kt CO₂/km², for a total of approximately 20 Gt CO₂. This represents the theoretical storage capacity limit that would be attained if there would be no other gases present in the coals or they would be 100% replaced by CO₂, and if all the coals will be accessed by CO₂. A recovery factor of less than 100% and a completion factor less than 50% reduce the theoretical storage capacity to an effective storage capacity of only 6.4 Gt CO₂. Not all the effective CO₂ storage capacity will be utilized because it is uneconomic to build the necessary infrastructure for areas with low storage capacity per unit surface. Assuming that the economic threshold to develop the necessary infrastructure is 200 kt CO₂/km², then the CO₂ storage capacity in coal beds in Alberta is greatly reduced further to a practical capacity of only ∼800 Mt CO₂.     

Study of inexpensive oxygen carriers for chemical looping combustion

Norwegian industrial tailings and by-products, as well as naturally occurring minerals and ores have been surveyed with the purpose of identifying candidate oxygen carrier materials for use in a chemical looping combustion process. Nine materials, based on manganese and/or iron oxide, were selected for an initial screening test; six were deemed promising and were hence investigated further. Thermogravimetric experiments were performed to investigate the oxygen capacity, the reaction kinetics and reversibility of the oxygen absorption reaction. A manganese ore with a reversible capacity of 4.9 wt% oxygen at 1000 °C was selected as the most promising for chemical looping combustion applications. This material was modified by addition of calcia to explore the possibility of enhancing the kinetic, catalytic and mechanical properties. The addition of excess calcium relative to manganese resulted in formation of calcium manganite and related phases. The oxygen capacity of the modified material was 4.5 wt% at 1000 °C, but it has potential advantages in terms of kinetics and chemical and mechanical stability relative to the pure ore.     

Farmland damage and its impact on the overlapped areas of cropland and coal resources in the eastern plains of China

The subsidence caused by coal mining in areas where cropland and coal resources overlap in the eastern plains of China with high ground water levels has caused large amounts of water to collect in cropland, significant damage to cropland, and a sharp contradiction between people and land distribution within this region. Systematic analysis and calculation were conducted on these areas by using GIS spatial overlay analysis technology, subsidence and occupied cropland estimation models, and crop yield reduction prediction model to reveal the overlapped characteristics and extent of farmland damage, as well as to evaluate the effects of farmland damage to grain yield, farmland landscape, agricultural population, and dynamical equilibrium of the total cultivated land. Results showed that the overlapped areas of cropland and coal resources on the eastern plains of China occupied an area covering 1.33 × 10⁵ km², which accounted for 31.93% of the total cropland area. In 2020, the accumulative total area of destroyed cropland reached 3.83 × 10³ km², thus reducing grain yield by 9.63 × 10⁸ kg, and increasing the number of landless farmers to 1.91 × 10⁶. Furthermore, the quality and production capacity of cultivated land decreased, farmland landscape patterns changed, land patterns and structures were adjusted, the dynamical equilibrium of the total cultivated land was difficult to guarantee, and social instability increased in coal mining subsidence areas. These findings provided a scientific basis for relevant government departments to enact countermeasures for the coordinative production of coal and grain.     

Chemical-looping combustion using syngas as fuel

Chemical-looping combustion (CLC) is a combustion technology where an oxygen carrier is used to transfer oxygen from the combustion air to the fuel, avoiding direct contact between air and fuel. Thus, CO₂ and H₂O are inherently separated from the rest of the flue gases and the carbon dioxide can be obtained in a pure form without the use of an energy intensive air separation unit. The paper presents results from a 3-year project devoted to developing the CLC technology for use with syngas from coal gasification. The project has focused on: (i) the development of oxygen carrier particles, (ii) establishing a reactor design and feasible operating conditions and (iii) construction and operation of a continuously working hot reactor. Approximately, 300 different oxygen carriers based on oxides of the metals Ni, Fe, Mn and Cu were investigated with respect to parameters, which are important in a CLC system, and from these investigations, several particles were found to possess suitable qualities as oxygen carriers. Several cold-model prototypes of CLC based on interconnected fluidized bed reactors were tested, and from these tests a hot prototype CLC reactor system was constructed and operated successfully using three carriers based on Ni, Fe and Mn developed within the project. The particles were used for 30–70 h with combustion, but were circulated under hot conditions for 60–150 h.     

Analytical solution for Joule–Thomson cooling during CO2 geo-sequestration in depleted oil and gas reservoirs

Mathematical tools are needed to screen out sites where Joule–Thomson cooling is a prohibitive factor for CO₂ geo-sequestration and to design approaches to mitigate the effect. In this paper, a simple analytical solution is developed by invoking steady-state flow and constant thermophysical properties. The analytical solution allows fast evaluation of spatiotemporal temperature fields, resulting from constant-rate CO₂ injection. The applicability of the analytical solution is demonstrated by comparison with non-isothermal simulation results from the reservoir simulator TOUGH2. Analysis confirms that for an injection rate of 3 kg s^?1 (0.1 MT yr^?1) into moderately warm (>40 °C) and permeable formations (>10^?14 m² (10 mD)), JTC is unlikely to be a problem for initial reservoir pressures as low as 2 MPa (290 psi).     

Treatment of municipal wastewater using a contact oxidation filtration separation integrated bioreactor

A new contact oxidation filtration separation integrated bioreactor (CFBR) was used to treat municipal wastewater. The CFBR was made up of a biofilm reactor (the upper part of the CFBR) and a gravitational filtration bed (the lower part of the CFBR). Polyacrylonitrile balls (50 mm diameter, 237 m²/m³ specific surface, 90% porosity, and 50.2% packing rate) were filled into the biofilm reactor as biofilm attaching materials and anthracite coal (particle size 1–2 mm, packing density 0.947 g/cm³, non-uniform coefficient (K₈₀ = d₈₀/d₁₀) < 2.0) was placed into the gravitational filtration bed as filter media. At an organic volumetric loading rate of 2.4 kg COD/(m³ d) and an initial filtration velocity of 5 m/h in the CFBR, the average removal efficiencies of COD, ammonia nitrogen, total nitrogen and turbidity were 90.6%, 81.4%, 64.6% and 96.7% respectively, but the treatment process seemed not to be effective in phosphorus removal. The average removal efficiency of total phosphorus was 60.1%. Additionally, the power consumption of the CFBR was less than 0.15 kWh/m³ of wastewater treated, and less than 1.5 kWh/kg BOD₅ removal.     

Effect of gas composition in Chemical-Looping Combustion with copper-based oxygen carriers: Fate of light hydrocarbons

Chemical-Looping Combustion (CLC) is an emerging technology for CO₂ capture because separation of this gas from the other flue gas components is inherent to the process and thus no energy is expended for the separation. Natural or refinery gas can be used as gaseous fuels and they may contain different amounts of light hydrocarbons. This paper presents the combustion results obtained with a Cu-based oxygen carrier using mixtures of CH₄ and light hydrocarbons (LHC) (C₂H₆ and C₃H₈) as fuel. The effect on combustion efficiency of the fuel reactor temperature, solid circulation flow rate and gas composition was studied in a continuous CLC plant (500 W_th). Full combustions were reached at 1073 and 1153 K working at oxygen to fuel ratios, ? higher than 1.5 and 1.2 respectively. Unburnt hydrocarbons were never detected at any experimental conditions at the fuel reactor outlet. Carbon formation can be avoided working at 1153 K or at ? values higher than 1.5 at 1073 K. After 30 h of continuous operation, the oxygen carrier exhibited an adequate behavior regarding attrition and agglomeration. It can be concluded that no special measures should be taken in a CLC process with Cu-based OC with respect to the presence of LHC in the fuel gas.     

Approaches for analyzing local carbon mitigation strategies: Tompkins County,New York,USA

A carbon budget was calculated for Tompkins County, NY, a semi-rural upstate county with a population density of 78 pp/km². The costs and potential for several carbon mitigation options were analyzed in four categories: terrestrial C sequestration, local power generation, transportation, and energy end-use efficiency. This study outlines a methodology for conducting this type of local-scale analysis, including sources and calculations adaptable to different localities. Effective carbon mitigation strategies for this county based on costs/Mg C and maximum potential include reforestation of abandoned agricultural lands, biomass production for residential heating and co-firing in coal power plants, changes in personal behavior related to transportation (e.g., public transportation), installation of residential energy efficient products such as programmable thermostats or compact fluorescent light bulbs, and development of local wind power. The total county emissions are about 340 Gg C/year, with biomass sequestration rates of 121 Gg C/year. The potential for mitigation, assuming full market penetration, amounts to about 234 Gg C/year (69%), with 100 Gg C/year (29%) at no net cost to the consumer. The development of local-scale C mitigation plans based on this sort of model of analysis is feasible and would be useful for guiding investments in climate change prevention.     

Assessment of basin-scale hydrologic impacts of CO2 sequestration,Illinois basin

Idealized, basin-scale sharp-interface models of CO₂ injection were constructed for the Illinois basin. Porosity and permeability were decreased with depth within the Mount Simon Formation. Eau Claire confining unit porosity and permeability were kept fixed. We used 726 injection wells located near 42 power plants to deliver 80 million metric tons of CO₂/year. After 100 years of continuous injection, deviatoric fluid pressures varied between 5.6 and 18 MPa across central and southern part of the Illinois basin. Maximum deviatoric pressure reached about 50% of lithostatic levels to the south. The pressure disturbance (>0.03 MPa) propagated 10–25 km away from the injection wells resulting in significant well–well pressure interference. These findings are consistent with single-phase analytical solutions of injection. The radial footprint of the CO₂ plume at each well was only 0.5–2 km after 100 years of injection. Net lateral brine displacement was insignificant due to increasing radial distance from injection well and leakage across the Eau Claire confining unit. On geologic time scales CO₂ would migrate northward at a rate of about 6 m/1000 years. Because of paleo-seismic events in this region (M5.5–M7.5), care should be taken to avoid high pore pressures in the southern Illinois basin.     

Operating experience with chemical looping combustion in a 120 kW dual circulating fluidized bed (DCFB) unit

This study presents first operating experience with a 120 kW chemical looping pilot rig. The dual circulating fluidized bed reactor system and its auxiliary units are discussed. Two different oxygen carriers, i.e. ilmenite, which is a natural iron titanium ore, and a designed Ni-based particle, are tested in the CLC unit. The pilot rig is fueled with H₂, CO and CH₄ respectively at a fuel power of 65–145 kW. High solids circulation, very low solids residence time and low solids inventory are observed during operation. Owing to the scalability of the design concept, these characteristics should be quite similar to those of commercial CLC power plants. Ilmenite shows a high potential for the combustion of H₂-rich gases (e.g. from coal gasification with steam). The H₂ conversion is quite high but there is still a high potential for further improvement. The Ni-based oxygen carrier achieves the thermodynamic maximum H₂ and CO conversion and also very high CH₄ conversion. A variation of the air/fuel ratio and the reaction temperature indicates that the Ni/NiO ratio of the particle has an influence on the performance of the chemical looping combustor. Generally, low solids conversion in air and fuel reactors is observed in almost any conditions. Despite a very low H₂O/CH₄ molar ratio, no carbon formation is observed.