Numerical simulation of chemical looping combustion process with CaSO4 oxygen carrier

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. The technique involves the use of an oxygen carrier which transfers oxygen from combustion air to the fuel, and hence a direct contact between air and fuel is avoided. A chemical-looping combustion system consists of a fuel reactor and an air reactor. A metal oxide is used as oxygen carrier that circulates between the two reactors. The air reactor is a high velocity fluidized bed where the oxygen carrier particles are transported together with the air stream to the top of the air reactor, where they are then transferred to the fuel reactor using a cyclone. The fuel reactor is a bubbling fluidized bed reactor where oxygen carrier particles react with hydrocarbon fuel and get reduced. The reduced oxygen carrier particles are transported back to the air reactor where they react with oxygen in the air and are oxidized back to metal oxide. The exhaust from the fuel reactor mainly consists of CO₂ and water vapor. After condensation of the water in the exit gas from the fuel reactor, the remaining CO₂ gas is compressed and cooled to yield liquid CO₂, which can be disposed of in various ways.With the improvement of numerical methods and more advanced hardware technology, the time needed to run CFD (Computational fluid dynamics) codes is decreasing. Hence multiphase CFD-based models for dealing with complex gas-solid hydrodynamics and chemical reactions are becoming more accessible. Until now there were a few literatures about mathematical modeling of chemical-looping combustion using CFD approach. In this work, the reaction kinetics model of the fuel reactor (CaSO₄ + H₂) was developed by means of the commercial code FLUENT. The bubble formation and the relation between bubble formation and molar fraction of products in gas phase were well captured by CFD simulation. Computational results from the simulation also showed low fuel conversion rate. The conversion of H₂ was about 34% partially due to fast, large bubbles rising through the reactor, low bed temperature and large particles diameter.     

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

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 sulphur compounds, such as H₂S and COS. This paper presents the combustion results obtained with a Cu-based oxygen carrier using mixtures of CH₄ and H₂S as fuel. The influence of H₂S concentration on the gas product distribution and combustion efficiency, sulphur splitting between the fuel reactor (FR) and the air reactor (AR), oxygen carrier deactivation and material agglomeration was investigated in a continuous CLC plant (500 W_th). The oxygen carrier to fuel ratio, ?, was the main operating parameter affecting the CLC system. Complete fuel combustion were reached at 1073 K working at ? values ≥1.5. The presence of H₂S did not produce a decrease in the combustion efficiency even when working with a fuel containing 1300 vppm H₂S. At these conditions, the great majority of the sulphur fed into the system was released in the gas outlet of the FR as SO₂, affecting to the quality of the CO₂ produced. Formation of copper sulphide, Cu₂S, and the subsequent reactivity loss was only detected working at low values of ? ≤ 1.5, although this fact did not produce any agglomeration problem in the fluidized beds. In addition, the oxygen carrier was fully regenerated in a H₂S-free environment. It can be concluded that Cu-based oxygen carriers are adequate materials to be used in a CLC process using fuels containing H₂S although quality of the CO₂ produced is affected.     

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.     

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.     

Reduction of CaSO4 oxygen carrier with coal in chemical-looping combustion: Effects of temperature and gasification intermediate

Chemical-looping combustion (CLC) has been suggested as an energy efficient method for the capture of carbon dioxide from combustion. Thermodynamics and kinetics of CaSO₄ reduction with coal via gasification intermediate in a CLC process were discussed in the paper, with respect to the CO₂ generating efficiency, the environmental factor and the surface morphology of oxygen carrier. Tests on the combined process of coal gasification and CaSO₄ reduction with coal syngas were conducted in a batch fluidized bed reactor at different reaction temperatures and with different gasification intermediates. The products were characterized by gas chromatograph, gas analyzers and scanning electron microscope. And the results showed that an increase in the reaction temperature aggravated the SO₂ emission. The CO₂ generating efficiency also increased with the temperature, but it decreased when the temperature exceeded 950 °C due to the sintering of oxygen carrier particles. The use of CO₂ as gasification intermediate in the fuel reactor had a positive effect on the sintering-resistant of oxygen carrier particles. However, increasing the steam/CO₂ ratio in gasification intermediate evidently enhanced CO₂ generating efficiency and reduced SO₂ environmental impact.     

Waste products from the steel industry with NiO as additive as oxygen carrier for chemical-looping combustion

Fe₂O₃-containing waste materials from the steel industry are proposed as oxygen carrier for chemical-looping combustion. Three such materials, red iron oxide, brown iron oxide and iron oxide scales, have been examined by oxidation and reduction experiments in a batch fluidized-bed reactor at temperatures between 800 and 950 °C. NiO-based particles have been used as additive, in order to examine if it is possible to utilize the catalytic properties of metallic Ni to facilitate decomposition of hydrocarbons into more reactive combustion intermediates such as CO and H₂. The experiments indicated modest reactivity between the waste materials and CH₄, which was used as reducing gas. Adding small amounts of NiO-based particles to the sample increased the yield of CO₂ in a standard experiment, typically by a factor of 1.5–3.5. The fraction of unconverted fuel typically was reduced by 70–90%. The conversion of CH₄ to CO₂ was 94% at best, corresponding to a combustion efficiency of 96%. This was achieved using a bed mass corresponding to 57 kg oxygen carrier per MW fuel, of which only 5 wt% was NiO-based synthetic particles. The different materials fared differently well during the experiments. Red iron oxide was fairly stable, while brown iron oxide was soft and subject to considerable erosion. Iron oxide scales experienced increased reactivity and porosity as function of the numbers of reduction cycles.     

Biogas combustion in a chemical looping fluidized bed reactor

Chemical looping combustion (CLC) is a process in which oxygen required for combustion of a fuel is supplied by the metal oxide. Metal oxide plays the role of an oxygen carrier by providing oxygen for combustion when being reduced and is then re-oxidized by air in a separate reactor. Combustion is thus without any direct contact between air and fuel: as a consequence flue gas does not contain nitrogen of air which simplifies flue gas treatment prior to sequestration. In the present study, biogas combustion was analyzed in a chemical looping combustion fluidized bed reactor. NiAl_0.44O_1.67 and Cu_0.95Fe_1.05AlO₄ metal oxide particles were used as oxygen carriers. The experiments have shown the feasibility of biogas combustion in chemical looping combustion: CH₄ of the biogas was completely converted to CO₂ and H₂O with a small fraction of CO and H₂. The outlet flue gas distribution profile was not affected by ageing during the cycles of reduction and oxidation, indicating the chemical stability of the oxygen carriers. There was limited formation of carbon on the oxygen carriers during reduction.     

Chemical-looping with oxygen uncoupling for combustion of solid fuels

Chemical-looping with oxygen uncoupling (CLOU) is a novel method to burn solid fuels in gas-phase oxygen without the need for an energy intensive air separation unit. The carbon dioxide from the combustion is inherently separated from the rest of the flue gases. CLOU is based on chemical-looping combustion (CLC) and involves three steps in two reactors, one air reactor where a metal oxide captures oxygen from the combustion air (step 1), and a fuel reactor where the metal oxide releases oxygen in the gas-phase (step 2) and where this gas-phase oxygen reacts with a fuel (step 3). In other proposed schemes for using chemical-looping combustion of solid fuels there is a need for an intermediate gasification step of the char with steam or carbon dioxide to form reactive gaseous compounds which then react with the oxygen carrier particles. The gasification of char with H₂O and CO₂ is inherently slow, resulting in slow overall rates of reaction. This slow gasification is avoided in the proposed process, since there is no intermediate gasification step needed and the char reacts directly with gas-phase oxygen. The process demands an oxygen carrier which has the ability to react with the oxygen in the combustion air in the air reactor but which decomposes to a reduced metal oxide and gas-phase oxygen in the fuel reactor. Three metal oxide systems with suitable thermodynamic properties have been identified, and a thermal analysis has shown that Mn₂O₃/Mn₃O₄ and CuO/Cu₂O have suitable thermodynamic properties, although Co₃O₄/CoO may also be a possibility. However, the latter system has the disadvantage of an overall endothermic reaction in the fuel reactor. Results from batch laboratory fluidized bed tests with CuO and a gaseous and solid fuel are presented. The reaction rate of petroleum coke is approximately a factor 50 higher using CLOU in comparison to the reaction rate of the same fuel with an iron-based oxygen carrier in normal CLC.     

Design study of a 150 kWth double loop circulating fluidized bed reactor system for chemical looping combustion with focus on industrial applicability and pressurization

Nowadays the lab scale feasibility of the chemical looping combustion technology has been proved. This article deals with many of the design requirements that need to be fulfilled to make this technology applicable at industrial scale. A design for a 150 kW_th chemical looping combustion reactor system is proposed. In the base case it is supposed to work with gaseous fuels and inexpensive oxygen carriers derived from industrial by-products or natural minerals. More specifically the fuel will be methane and a manganese ore will be the basis for the oxygen carrier. It is a double loop circulating fluidized bed where both the air reactor and the fuel reactor are capable to work in the fast fluidization regime in order to increase the gas solids contact along the reactor body. High operational flexibility is aimed, in this way it will be possible to run with different fuels and oxygen carriers as well as different operating conditions such as variation in air excess. Compactness is a major goal in order to reduce the required solid material and possibly to enclose the reactor body into a pressurized vessel to investigate the chemical looping combustion under pressurized conditions. The mass and heat balance are described, as well as the hydrodynamic investigations performed. Most design solutions presented are taken from industrial standards as one main objective is to meet commercial requirements.     

160 h of chemical-looping combustion in a 10 kW reactor system with a NiO-based oxygen carrier

Chemical-looping combustion, CLC, is a technology with inherent separation of the greenhouse gas CO₂. The technique uses an oxygen carrier made up of particulate metal oxide to transfer oxygen from combustion air to fuel. In this work, an oxygen carrier consisting of 60% NiO and 40% NiAl₂O₄ was used in a 10 kW CLC reactor system for 160 h of operation with fuel. The first 3 h of fuel operation excepted, the test series was accomplished with the same batch of oxygen carrier particles. The fuel used in the experiments was natural gas, and a fuel conversion to CO₂ of approximately 99% was accomplished. Combustion conditions were very stable during the test period, except for the operation at sub-stoichiometric conditions. It was shown that the methane fraction in the fuel reactor exit gas was dependent upon the rate of solids circulation, with higher circulation leading to more unconverted methane. The carbon monoxide fraction was found to follow the thermodynamical equilibrium for all investigated fuel reactor temperatures, 660–950 °C. Thermal analysis of the fuel reactor at stable conditions enabled calculation of the particle circulation which was found to be approximately 4 kg/s, MW. The loss of fines, i.e. the amount of elutriated oxygen carrier particles with diameter <45 μm, decreased during the entire test period. After 160 h of operation the fractional loss of fines was 0.00022 h⁻¹, corresponding to a particle life time of 4500 h.     

Solid fuels in chemical-looping combustion

The feasibility of using a number of different solid fuels in chemical-looping combustion (CLC) has been investigated. A laboratory fluidized bed reactor system for solid fuel, simulating a chemical-looping combustion system by exposing the sample to alternating reducing and oxidizing conditions, was used. In each reducing phase 0.2 g of fuel in the size range 180–250 μm was added to the reactor containing 40 g oxygen carrier of size 125–180 μm. Two different oxygen carriers were tested, a synthetic particle of 60% active material of Fe₂O₃ and 40% MgAl₂O₄ and a particle consisting of the natural mineral ilmenite. Effect of steam content in the fluidizing gas of the reactor was investigated as well as effect of temperature. A number of experiments were also made to investigate the rate of conversion of the different fuels in a CLC system. A high dependency on steam content in the fluidizing gas as well as temperature was shown. The fraction of volatiles in the fuel was also found to be important. Furthermore the presence of an oxygen carrier was shown to enhance the conversion rate of the intermediate gasification reaction. At 950 °C and with 50% steam the time needed to achieve 95% conversion of fuel particles with a diameter of 0.125–0.18 mm ranged between 4 and 15 min depending on the fuel, while 80% conversion was reached within 2–10 min. In almost all cases the synthetic Fe₂O₃ particle with 40% MgAl₂O₄ and the mineral ilmenite showed similar results with the different fuels.     

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.     

Development and testing of AZEP reactor components

The advanced zero emissions power plant (AZEP) project addresses the development of a novel “zero emissions,” gas turbine-based, power generation process to reduce local and global CO₂ emissions in a cost-effective way.The key element in AZEP is an integrated MCM-reactor, in which (a) O₂ is separated from air by means of a mixed-conducting membrane (MCM), (b) combustion of natural gas occurs in an N₂-free environment and (c) the heat of combustion is transferred to air by heat exchange.This paper focuses on the development and testing of the ceramic components of the MCM-reactor (air separation membrane and heat exchangers). For compactness and manufacturability, a module design based on extruded square channel monoliths has been chosen. The manifold design enables gas distribution in a checkerboard pattern. Modules with contact area of >500 m²/m³ have been produced.Results from testing of the modules under close to realistic process conditions agree with model predictions. Extrapolation to AZEP process conditions gives an oxygen production rate of around 37 mol O₂/(m³ s), or 15 MW/m³ power density (per net MCM volume). These values correspond to project targets and confirm the feasibility of the AZEP concept.     

Multi-stage chemical looping combustion (CLC) for combined cycles with CO2 capture

This paper presents application of the chemical looping combustion (CLC) method in natural gas-fired combined cycles for power generation with CO₂ capture. A CLC combined cycle consisting of single CLC-reactor system, an air turbine, a CO₂-turbine and a steam cycle has been designated as the base-case cycle. The base-case cycle can achieve net plant efficiency of about 52% at an oxidation temperature of 1200 °C. In order to achieve a reasonable efficiency at lower oxidation temperatures, reheat is introduced into the air turbine by employing multi CLC-reactors. The results show that the single reheat CLC-combined cycle can achieve net plant efficiency of above 51% at oxidation temperature of 1000 °C and above 53% at the oxidation temperature of 1200 °C including CO₂ compression to 110 bar. The double reheat cycle results in marginal efficiency improvement as compared to the single reheat cycle. The CLC-cycles are also compared with a conventional combined cycle with and without post-combustion capture in amine solution. All the CLC-cycles show higher net plant efficiencies with close to 100% CO₂ capture as compared to a conventional combined cycle with post-combustion capture, which is very promising.     

Assessment of the different parameters affecting the CO2 purity from coal fired oxyfuel process

The oxyfuel process is one of the most promising options to capture CO₂ from coal fired power plants. The combustion takes place in an atmosphere of almost pure oxygen, delivered from an air separation unit (ASU), and recirculated flue gas. This provides a flue gas containing 80–90 vol% CO₂ on a dry basis. Impurities are caused by the purity of the oxygen from the ASU, the combustion process and air ingress. Via liquefaction a CO₂ stream with purity in the range from 85 to 99.5 vol% can be separated and stored geologically. Impurities like O₂, NO_X, SO_X, and CO may negatively influence the transport infrastructure or the geological storage site by causing geochemical reactions. Therefore the maximum acceptable concentrations of the impurities in the separated CO₂ stream must be defined regarding the requirements from transportation and storage. The main objective of the research project COORAL therefore is to define the required CO₂ purity for capture and storage.     

Investigation of NiO/NiAl2O4 oxygen carriers for chemical-looping combustion produced by spray-drying

Chemical-looping combustion is a novel combustion technology with inherent separation of the greenhouse gas CO₂. The technology uses circulating oxygen carriers to transfer oxygen from the combustion air to the fuel. In this paper, oxygen carriers based on commercially available NiO and α-Al₂O₃ were prepared using the industrial spray-drying method, and compared with particles prepared by freeze-granulation. The materials were investigated under alternating oxidizing and reducing conditions in a laboratory fluidized bed, thus simulating the cyclic conditions of a chemical-looping combustion system. The particles produced by spray-drying displayed a remarkable similarity to the freeze-granulated oxygen carriers, with high reactivity when the bed was fluidized and similar physical properties when sintered at the same temperature. This is an important result as it shows that the scaling-up from a laboratory production method, i.e. freeze-granulation, to a commercial method suitable for large-scale production, i.e. spray-drying, did not involve any unexpected difficulties. A difference noticed between the spray-dried and freeze-granulated particles was the sphericity. Whereas the freeze-granulated particles showed near perfect sphericity, a large portion of the spray-dried particles had hollow interiors. Defluidization was most likely to occur for highly reduced particles, at low gas velocities. The apparent density and crushing strength of the oxygen carriers could be increased either by increasing the sintering temperature or by increasing the sintering time. However, the fuel conversion was fairly unchanged when the sintering temperature was increased but was clearly improved when the sintering time was increased.     

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.     

CO2 capture from combined cycles integrated with Molten Carbonate Fuel Cells

In this paper Molten Carbonate Fuel Cells (MCFCs) are considered for their potential application in carbon dioxide separation when integrated into natural gas fired combined cycles. The MCFC performs on the anode side an electrochemical oxidation of natural gas by means of CO₃^2? ions which, as far as carbon capture is concerned, results in a twofold advantage: the cell removes CO₂ fed at the cathode to promote carbonate ion transport across the electrolyte and any dilution of the oxidized products is avoided.The MCFC can be “retrofitted” into a combined cycle, giving the opportunity to remove most of the CO₂ contained in the gas turbine exhaust gases before they enter the heat recovery steam generator (HRSG), and allowing to exploit the heat recovery steam cycle in an efficient “hybrid” fuel cell + steam turbine configuration. The carbon dioxide can be easily recovered from the cell anode exhaust after combustion with pure oxygen (supplied by an air separation unit) of the residual fuel, cooling of the combustion products in the HRSG and water separation. The resulting power cycle has the potential to keep the overall cycle electrical efficiency approximately unchanged with respect to the original combined cycle, while separating 80% of the CO₂ otherwise vented and limiting the size of the fuel cell, which contributes to about 17% of the total power output so that most of the power capacity relies on conventional low cost turbo-machinery. The calculated specific energy for CO₂ avoided is about 4 times lower than average values for conventional post-combustion capture technology. A sensitivity analysis shows that positive results hold also changing significantly a number of MCFC and plant design parameters.     

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.     

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.