Differences in reactivity of pulverised coal in air (O2/N2) and oxy-fuel (O2/CO2) conditions

The reactivity of four pulverised Australian coals were measured under simulated air (O₂/N₂) and oxy-fuel (O₂/CO₂) environments using a drop tube furnace (DTF) maintained at 1673 K and a thermogravimetric analyser (TGA) run under non-isothermal (heating) conditions at temperatures up to 1473 K. The oxygen concentration, covering a wide and practical range, was varied in mixtures of O₂/N₂ and O₂/CO₂ in the range of 3 to 21 vol.% and 5 to 30 vol.%, respectively. The apparent volatile yield measured in CO₂ in the DTF was greater than in N₂ for all the coals studied. Pyrolysis experiments in the TGA also revealed an additional mass loss in a CO₂ atmosphere, not observed in a N₂ atmosphere, at relatively high temperatures. The coal burnout measured in the DTF at several O₂ concentrations revealed significantly higher burnouts for two coals and similar burnouts for the other two coals in oxy-fuel conditions. TGA experiments with char also revealed higher reactivity at high temperatures and low O₂ concentration. The results are consistent with a char–CO₂ reaction during the volatile yield experiments, but additional experiments are necessary to resolve the mechanisms determining the differences in coal burnout.     

In situ diagnostics of Victorian brown coal combustion in O2/N2 and O2/CO2 mixtures in drop-tube furnace

Experimental investigation of the combustion of an air-dried Victorian brown coal in O₂/N₂ and O₂/CO₂ mixtures was conducted in a lab-scale drop-tube furnace (DTF). In situ diagnostics of coal burning transient phenomena were carried out with the use of high-speed camera and two-colour pyrometer for photographic observation and particle temperature measurement, respectively. The results indicate that the use of CO₂ in place of N₂ affected brown coal combustion behaviour through both its physical influence and chemical interaction with char. Distinct changes in coal pyrolysis behaviour, ignition extent, and the temperatures of volatile flame and burning char particles were observed. The large specific heat capacity of CO₂ relative to N₂ is the principal factor affecting brown coal combustion, which greatly quenched the ignition of individual coal particles. As a result, a high O₂ fraction of at least 30% in CO₂ is required to match air. Moreover, due to the accumulation of unburnt volatiles in the coal particle vicinity, coal ignition in O₂/CO₂ occurred as a form of volatile cloud rather than individual particles that occurred in air. The temperatures of volatile flame and char particles were reduced by CO₂ quenching throughout coal oxidation. Nevertheless, this negative factor was greatly offset by char-CO₂ gasification reaction which even occurred rapidly during coal pyrolysis. Up to 25% of the nascent char may undergo gasification to yield extra CO to improve the reactivity of local fuel/O₂ mixture. The subsequent homogeneous oxidation of CO released extra heat for the oxidation of both volatiles and char. As a result, the optical intensity of volatile flame in ∼27% O₂ in CO₂ was raised to a level twice that in air at the furnace temperature of 1273 K. Similar temperatures were achieved for burning char particles in 27% O₂/73% CO₂ and air. As this O₂/CO₂ ratio is lower than that for bituminous coal, 30-35%, a low consumption of O₂ is desirable for the oxy-firing of Victorian brown coal. Nevertheless, the distinct emission of volatile cloud and formation of strong reducing gas environment on char surface may affect radiative heat transfer and ash formation, which should be cautioned during the oxy-fuel combustion of Victorian brown coal.     

Experimental investigation of the combustion of bituminous coal in air and O2/CO2 mixtures: 2. Variation of the transformation behaviour of mineral matter with bulk gas composition

Combustion of a Chinese bituminous coal was carried out in a laboratory-scale drop tube furnace (DTF) to clarify the variation of ash properties with bulk gas composition. The combustion conditions tested include three bulk gases, air, 21% O₂/79% CO₂ and 27% O₂/73% CO₂, two furnace/gas temperatures close to the fluidized bed reactor temperature range, 1073 K and 1273 K, and three particle residence times. Apart from bulk properties analysis, individual ash particles and the original mineral species in coal were characterized using Computer - Controlled Scanning Electron Microscopy (CCSEM). The results indicate that, under the given experimental conditions, shifting bulk gas from air to O₂/CO₂ mixtures is insignificant in terms of the elemental composition of bulk ash, in agreement with the literature. However, changes in the properties of individual species/metals are noticeable, including the extent of the vaporization of volatile elements, ash particle-size distribution (PSD), crystallization extent of K alumino-silicate associate, pyrite decomposition and oxidation rate and formation propensity of liquidus in ash. These changes were mostly considered to be caused by the evolution of included mineral grains in the distinct char particles in the O₂/CO₂ environment. Reduction in char particle temperature with bulk gas shifting from air to O₂/CO₂ mixtures was primarily crucial, which, however, could be overweighed by the existence of a fairly strong local reducing condition on the char surface in O₂/CO₂. Consequently, vaporization of the volatile elements such as Na and P was promoted; formation of the crystalline leucite in air was in contrast inhibited. Furthermore, the extent of coalescence of included minerals and oxidation rate of pyrite (or its derivative, pyrrhotite) were also influenced by char consumption rate, i.e. the receding extent of char surface. These parameters exerted a combined effect on ash formation, requiring detailed mathematical modeling to describe the dynamics of the formation of oxy-fuel ash. This study also indicated that the differences of ash properties formed between air and O₂/CO₂ mixtures can be greatly reduced and eventually eliminated by increasing furnace temperature. Increase in the turbulence of gas flow should also benefit the elimination of the side effects of local reducing gases on char surface.     

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.     

Pulverized coal combustion in air and in O2/CO2 mixtures with NOx recycle

This paper presents experimental results of a 20 kW vertical combustor equipped with a single pf-burner on pulverised coal combustion in air and O₂/CO₂ mixtures with NO_x recycle. Experimental results on combustion performance and NO_x emissions of seven international bituminous coals in air and in O₂/CO₂ mixtures confirm the previous findings of the authors that the O₂ concentration in the O₂/CO₂ mixture has to be 30% or higher to produce matching temperature profiles to those of coal-air combustion while coal combustion in 30% O₂/70% CO₂ leads to better coal burnout and less NO_x emissions than coal combustion in air. Experimental results with NO_x recycle reveal that the reduction of the recycled NO depends on the combustion media, combustion mode (staging or non-staging) and recycling location. Generally, more NO is reduced with coal combustion in 30% O₂/70% CO₂ than with coal combustion in air. Up to 88 and 92% reductions of the recycled NO can be achieved with coal combustion in air and in 30% O₂/70% CO₂ respectively. More NO is reduced with oxidant staging than without oxidant staging when NO is recycled through the burner. Much more NO is reduced when NO recycled through the burner (from 65 to 92%) than when NO is recycled through the staging tertiary oxidant ports (from 33 to 54%). The concentration of the recycled NO has little influence on the reduction efficiency of the recycled NO with both combustion media—air and 30% O₂/70% CO₂.     

Charged fraction and electrostatic collection of ultrafine and submicrometer particles formed during O2-CO2 coal combustion

The charged fraction of submicrometer and ultrafine particles generated during bench scale coal combustion and the subsequent penetration of particles through a cylindrical-wire electrostatic precipitator (ESP) in O₂-CO₂ and O₂-N₂ environments were measured. In all combustion environments, natural particle charging within the combustor was not adequate for high efficiency particle collection in the ESP; thus, corona generation was necessary for enhanced particle charging. With a positive applied potential, the corona inception voltage and voltage required to reach a given current level in the ESP in gas mixtures composed of O₂ and CO₂ were higher than those composed of O₂ and N₂, while similar voltages were needed for negative corona generation. In positive coronas, particle penetration through the ESP in O₂-CO₂ environments was 1-2 orders of magnitude higher than in O₂-N₂ environments. Little difference in particle penetration between O₂-N₂ and O₂-CO₂ was seen in negative coronas.     

Changes in char reactivity and structure during the gasification of a Victorian brown coal: Comparison between gasification in O2 and CO2

Char reactivity is an important factor influencing the efficiency of a gasification process. As a low-rank fuel, Victorian brown coal with high gasification reactivity is especially suitable for use with gasification-based technologies. In this study, a Victorian brown coal was gasified at 800 °C in a fluidised-bed/fixed-bed reactor. Two different gasifying agents were used, which were 4000 ppm O₂ balanced with argon and pure CO₂. The chars produced at different gasification conversion levels were further analysed with a thermogravimetric analyser (TGA) at 400 °C in air for their reactivities. The structural features of these chars were also characterised with FT-Raman/IR spectroscopy. The contents of alkali and alkaline earth metallic species in these chars were quantified. The reactivities of the chars prepared from the gasification in pure CO₂ at 800 °C were of a much higher magnitude than those obtained for the chars prepared from the gasification in 4000 ppm O₂ also at 800 °C. Even though both atmospheres (i.e. 4000 ppm O₂ and pure CO₂) are oxidising conditions, the results indicate that the reaction mechanisms for the gasification of brown coal char at 800 °C in these two gasifying atmospheres are different. FT-Raman/IR results showed that the char structure has been changed drastically during the gasification process.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

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.     

Coal devolatilization and char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of the present investigation is to examine differences between O₂/N₂ and O₂/CO₂ atmospheres during devolatilization and char conversion of a bituminous coal at conditions covering temperatures between 1173 K and 1673 K and inlet oxygen concentrations between 5 and 28 vol.%. The experiments have been carried out in an electrically heated entrained flow reactor that is designed to simulate the conditions in a suspension fired boiler. Coal devolatilized in N₂ and CO₂ atmospheres provided similar results regarding char morphology, char N₂-BET surface area and volatile yield. This strongly indicates that a shift from air to oxy-fuel combustion does not influence the devolatilization process significantly. Char combustion experiments yielded similar char conversion profiles when N₂ was replaced with CO₂ under conditions where combustion was primarily controlled by chemical kinetics. When char was burned at 1573 K and 1673 K a faster conversion was found in N₂ suggesting that the lower molecular diffusion coefficient of O₂ in CO₂ lowers the char conversion rate when external mass transfer influences combustion. The reaction of char with CO₂ was not observed to have an influence on char conversion rates at the applied experimental conditions.     

Modeling of NOx conversion during combustion under high CO2 concentration using detailed chemical kinetics

Combustion of fuels under enhanced oxygen atmospheres has been well investigated over the past decades in various types of combustors, varying from diesel engines to coal-fired boilers. Most studies have found significantly lower NO_x emissions during Oxy-coal combustion. In this paper, NO_x combustion chemistry under O₂/CO₂ atmosphere as well as air atmosphere was studied using detailed kinetic model. A suitable reaction mechanism was chosen based on the comparison between the calculation result and the experimental data. The influence of various parameters (temperature, CO₂ concentration) on NO_x conversion was investigated. The chemical effects of high CO₂ concentration on NO formation and destruction process was studied. On the basis of investigations through elementary chemical reactions, it can be concluded that high CO₂ concentration play a pronounced role on NO_x conversion process. Moreover, the dominant reaction steps contribution to production and destruction of NO as well as the most important reactions for NO reduction under different atmospheres were discussed.     

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.     

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.     

Spatial distributions of O2, CO2 and SO2 in a pilot-scale fluidized bed combustor operated with different coals

Axial concentration profiles of O₂, CO₂ and SO₂ have been measured at different radial positions in a coal-fired fluidized bed combustor. The profiles show some spatial inhomogeneity in the bed, the degree of which depends on fluidizing velocity and amount of excess air. Comparison of SO₂- with CO₂-concentration profiles reveals that SO₂ is formed in proportion to CO₂ only with anthracite as fuel. With bituminous coals, SO₂ is preferentially formed near the coal feed point. These results are discussed with regard to characteristic times of mixing and chemical reaction in fluidized beds, and SO₂-formation characteristics of the employed coals obtained in a thermobalance.     

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.     

Predictive equations for CO2 emission factors for coal combustion, their applicability in a thermal power plant and subsequent assessment of uncertainty in CO2 estimation

The emission of carbon dioxide varies systematically with the rank and type of coal combusted. Hence use of a single default emission factor proposed by IPCC (Inter Governmental Panel on Climate Change) for entire categories coals may not be appropriate option to obtain a reliable estimate of carbon dioxide emission level or towards the preparation of national carbon dioxide inventory. Even predictive equations developed based on the coals of different origin may not work well with coals of a specific origin. Several linear predictive equations were thus developed separately for coking and non-coking coals of Indian origin for the estimation of carbon dioxide emission utilizing basic coal parameters such as VM, FC, GCV and NCV on different basis. Large numbers of authenticated data set were used for multiple regression analysis and good correlations were obtained. Those equations were also validated with different data sets of Indian coals. Its applicability towards estimation of CO₂ emission from power plant was also studied and uncertainty in CO₂ estimation is revealed. The developed equations may be utilized to get a realistic estimate of carbon dioxide emission with specific cases where Indian coals are mostly used.     

Numerical investigation of the oxy-fuel combustion in large scale boilers adopting the ECO-Scrub technology

The present paper presents a three-dimensional numerical investigation of a pulverized-fuel, tangentially-fired utility boiler located at Florina/Greece under air, partial and full oxy-fuel conditions. Heat and mass transfer and major species concentration, such as CO₂, CO and O₂ are calculated; whilst the results for the reference air case scenario studied are in good agreement with the corresponding operational data measured in the plant, both for combustion calculations and NO_x emissions. Results for the partial and full oxy-fuel operation scenarios are in line with similar experimental and numerical investigations found in the recent literature. This numerical investigation of oxy-fuel conditions scenarios prior to their implementation under real scale conditions demonstrates the utmost of its importance, since significant results regarding the operation of a boiler in terms of lignite particle trajectories and burning rates are attained. Furthermore, NO_x calculations have been performed for all the examined case studies.     

Kinetic relationship between NO/N2O reduction and O2 consumption during flue-gas recycling coal combustion in a bubbling fluidized-bed

Flue-gas recycling combustion of a sub-bituminous coal and its rapid pyrolysis char at 1120 K has been simulated experimentally in a bubbling fluidized-bed. O₂, CO₂ and H₂O, and NO or N₂O were pre-mixed and fed into the bed together with coal/char particles with the O₂ concentration in the exit gas maintained at 3.5 vol%. Increasing the inlet O₂ concentration, thus increasing the O₂ consumption rate and decreasing the flue-gas recycling ratio, caused the once-through conversion of fuel-bound nitrogen into N₂O to decrease while the conversion to NO to remain unchanged. The in-bed reductions of NO and N₂O were both first order with respect to the respective nitrogen oxide, with the rate constants to increase linearly with the rate of O₂ consumption in the bed and thus also with that of char/volatiles consumption. This finding, which indicated linear increase in the concentrations of reactive species involved in NO/N₂O reduction with the rate of O₂ consumption, enabled consideration that the homogeneous and heterogeneous reduction rates of NO and N₂O were proportional to the consumption rates of O₂ by the volatiles and char, respectively. The rate analysis of the kinetic data revealed the relative importance of burning volatiles and char as the agents for the reduction of NO and N₂O. While the reduction in the gas phase was fully responsible for the NO-to-N₂O conversion, the reactions over the char surface governed the NO-to-N₂ reduction. The volatiles and char had comparable contributions to the reduction of N₂O to N₂. The NO-to-N₂ and N₂O-to-N₂ reductions over the char surface were, respectively, accelerated and decelerated by increasing the H₂O concentration.     

Ca-based sorbent looping combustion for CO2 capture in pilot-scale dual fluidized beds

To demonstrate process feasibility of in situ CO₂ capture from combustion of fossil fuels using Ca-based sorbent looping technology, a flexible atmospheric dual fluidized bed combustion system has been constructed. Both reactors have an ID of 100 mm and can be operated at up to 1000 °C at atmospheric pressure. This paper presents preliminary results for a variety of operating conditions, including sorbent looping rate, flue gas stream volume, CaO/CO₂ ratio and combustion mode for supplying heat to the sorbent regenerator, including oxy-fuel combustion of biomass and coal with flue gas recirculation to achieve high-concentration CO₂ in the off-gas. It is the authors' belief that this study is the first demonstration of this technology using a pilot-scale dual fluidized bed system, with continuous sorbent looping for in situ CO₂ capture, albeit at atmospheric pressure. A multi-cycle test was conducted and a high CO₂ capture efficiency (> 90%) was achieved for the first several cycles, which decreased to a still acceptable level (> 75%) even after more than 25 cycles. The cyclic sorbent was sampled on-line and showed general agreement with the features observed using a lab-scale thermogravimetric analysis (TGA) apparatus. CO₂ capture efficiency decreased with increasing number of sorbent looping cycles as expected, and sorbent attrition was found to be another significant factor to be limiting sorbent performance.     

CO2, NOx and SO2 emissions from the combustion of coal with high oxygen concentration gases

The emissions of CO₂, NO_x and SO₂ from the combustion of a high-volatile coal with N₂- and CO₂-based, high O₂ concentration (20, 50, 80, 100%) inlet gases were investigated in an electrically heated up-flow-tube furnace at elevated gas temperatures (1123–1573 K). The fuel equivalence ratio, φ, was varied in the range of 0.4–1.6. Results showed that CO₂ concentrations in flue gas were higher than 95% for the processes with O₂ and CO₂-based inlet gases. NO_x emissions increased with φ under fuel-lean conditions, then declined dramatically after φ=0.8, and the peak values increased from about 1000 ppm for the air combustion process and 500 ppm for the O₂(20%)+CO₂(80%) inlet gas process to about 4500 ppm for the oxygen combustion process. When φ>1.4 the emissions decreased to the same level for different O₂ concentration inlet gas processes. On the other hand, NO_x emission indexes decreased monotonically with φ under both fuel-lean and fuel-rich combustion. SO₂ emissions increased with φ under fuel-lean conditions, then declined slightly after φ>1.2. Temperature has a large effect on the NO_x emission. Peak values of the NO_x emission increased by 50–70% for the N₂-based inlet gas processes and by 30–50% for the CO₂-based inlet gas process from 1123 to 1573 K. However, there was only a small effect of temperature on the SO₂ emission.