Experimental study on N2O emission in O2/CO2 combustion with high oxygen concentration in circulating fluidized bed

To characterize the N₂O formation and fuel nitrogen conversion in an oxy-fuel circulating fluidized bed (CFB) combustor with high oxygen concentration, tests were carried out by analysing the axial concentrations of N₂O in a 50 kW_th CFB combustor. The conversion ratios from fuel nitrogen to gaseous N-containing pollutants were calculated. The initial N₂O concentrations in the bottom of the combustor were similar between oxy-fuel firing and air-firing. The axial N₂O formation was more in oxy-fuel combustion than in air-firing, improving the N₂O emission during 50% O₂/50% CO₂ combustion. The atmospheric variation significantly affected the conversion ratio from fuel nitrogen to N₂O. In addition, the conversion from fuel nitrogen to N₂O was much higher than that to NO. As a result, the N₂O emission during oxy-fuel CFB combustion cannot be ignored. Gas staging little influenced the N₂O emission. With the increasing ratio of secondary gas, the initial N₂O formation in the dense zone increased, while the axial N₂O formation along the combustor declined. By analysing the conversion ratios of fuel nitrogen, it was also found that gas staging obviously affected the conversion ratio from fuel nitrogen to NO by enhancing the NO to N₂ conversion. However, gas staging did not impact the conversion ratio from fuel nitrogen to N₂O.     

Formation and O2/CO2 combustion characteristics of real-environment coal char in high-temperature oxy-fuel conditions

Oxygen-fuel combustion is a promising technology for CO₂ emission reduction. The high-temperature entrained flow reactor and high-temperature drop tube furnace were used to analyses the formation and O₂/CO₂ combustion characteristics of real-environment coal char in high-temperature oxy-fuel conditions. It proposed “inflection point standard” of high-temperature flame method for the preparation of real-environmental oxy-fuel coal char according to the flame method. The results show that the ratios of C=O/C-O and C=O/C_ar increase in the coal char compared with the raw coals. The trend of C=O/C_ar in oxy-fuel condition is opposite to that in the inert atmosphere, due to the effect of high-concentration CO₂. To achieve the burnout rate similar to air combustion for coal char, with the increase of coal rank, the O₂ concentration should be enhanced. The optimal O₂ concentration for the oxy-fuel combustion of JC anthracite is 30%, while that of other low-rank coals could be lower than 30%. The combustion characteristic of JC anthracite is with the highest sensitivity to temperature and O₂ concentration.     

Experimental investigation on the conversion of fuel-N to NOx of quasi-particle in flue gas recirculation sintering process

Flue gas recirculation sintering process is a potential technology to decrease fuel consumption and NOx emissions compared with conventional sintering process. In present work, a vertical quartz tube reactor was used to investigate the combustion characteristics and conversion of fuel-N to NOx of quasi-particle. The mass conversion rate of quasi-particle increases with higher temperature. It was found that D₁ model is more appropriate than other models to describe quasi-particle combustion process through comparing correlation coefficients calculated by different mechanism models. Effects of temperature, coke size and proportion, circulating flue gas components on the conversion of fuel-N to NOx of quasi-particle were studied. The conversion rate of fuel-N to NOx of quasi-particle increases with higher temperature. With increasing coke size and proportion, the conversion rate of fuel-N to NOx decreases obviously. O₂ has a positive impact on the conversion of fuel-N to NOx of quasi-particle. CO could decrease the conversion rate of fuel-N to NOx by reducing NO directly or reacting with char to decrease NOx indirectly. CO₂ has an obviously inhibitory effect on the conversion of fuel-N to NOx of quasi-particle because it reacts with char to generate CO. The results were conducive to further understanding the combustion behavior and NOx formation mechanism of quasi-particle during flue gas recirculation sintering.     

Nitrogen transfer of fuel-N in chemical looping combustion

Chemical-looping combustion (CLC) is a novel technique used for CO₂ separation that has been investigated for gaseous fuel and solid fuel. The nitrogen transfer of fuel-N in the coal is experimentally investigated with a NiO/Al₂O₃ oxygen carrier under a continuous operation in a 1 kW_th interconnected fluidized bed prototype. The effects of the fuel reactor temperature, coal type and operation conditions on the release of gaseous products of nitrogen species in the air reactor and the fuel reactor are carried out. Results show that the nitrogen transfer direction of fuel-N is toward N₂ formation in the fuel reactor independent of fuel type. In the fuel reactor N₂ is the sole product of nitrogen transfer of fuel-N. The concentration of N₂ in the fuel reactor exit gas increases with the fuel reactor temperature. The NO_x precursor of HCN can be oxidized by the oxygen carrier to form NO or N₂ in the fuel reactor. However, in the fuel reactor NO from coal devolatilization and HCN oxidization by oxygen carrier is completely reduced to N₂. The other NO_x precursor of NH₃ is completely converted to N₂ due to oxidization by NiO and the catalytic effect of Ni on the decomposition of NH₃. After coal devolatilization, char-N conversion in the fuel reactor is toward N₂ formation according to the investigation of solid–solid reaction between char and oxygen carrier. The amount of residual char has a potential to cause formation of nitrogen contaminants in the air reactor. In the air reactor, NO is the only nitrogen contaminant, and there is no NO₂ formation. The high fuel reactor temperature results in little residual char coming into the air reactor. The proportion of char-N converted to NO in the air reactor increases from 16.98% to 18.85% when the fuel reactor temperature changes from 850 to 950 °C. For the fuels containing more volatile matter, the possibility of NO formation in the air reactor is smaller than the fuels containing less volatile matter. For the fuels containing less volatile matter, char gasification rate is still a significant factor both for the carbon capture efficiency and NO formation.     

Experimental investigation of combustion characteristics and NOx formation of coal particles using laser induced breakdown spectroscopy

To study the mechanism of coal combustion and NO_x formation, the combustion of coal particles in different atmospheres (O₂/N₂, O₂/CO₂) with different O₂ concentrations was investigated using the CO₂ laser as a heat source. The spatial distribution of atoms and groups (e.g., H at 656.2 nm, O at 777.3 nm, CN at 388.3 nm) relating to the combustion flame were measured simultaneously using laser induced breakdown spectroscopy (LIBS). The residual energy was measured during the collection of LIBS spectra in the combustion process, which could be characterized the temperature profiles of combustion flame due to the positive correlation with temperature. The combustion stage could be clearly discriminated by the emission of H and CN, along with the flame temperature. The residual energy obtained in different atmospheres indicated that the impact of combustion atmosphere on flame temperature is greater in the char combustion stage rather than volatile combustion stage. It was determined from the temporal and spatial distribution of residual energy and CN intensity that a higher flame temperature leads to a higher concentration of CN. The correlation between the generation of CN and the NO_x formation was also investigated to show that the formation approaches of NO_x are similar in the O₂/CO₂ and O₂/N₂ atmospheres, while the fuel-N conversion paths are different between volatile combustion and char combustion stages. The measurement of temporal and spatial distributions of LIBS spectra with varying flame temperatures is significant in revealing the mechanism of coal-particle combustion and NO_x formation.     

Experimental investigation of ignition and combustion characteristics of single coal and biomass particles in O2/N2 and O2/H2O

Oxy-steam combustion is a potential new-generation option for CO₂ capture and storage. The ignition and combustion characteristics of single coal and biomass particles were investigated in a flow tube reactor in O₂/N₂ and O₂/H₂O at various oxygen concentrations. The ignition and combustion processes were recorded using a CCD camera, and the two-color pyrometry was used to estimate the volatile flame temperature and char combustion temperature. In O₂/N₂ and O₂/H₂O, coal ignites heterogeneously at <O₂> = 21–50%. In O₂/N₂, biomass ignites homogeneously at <O₂> = 21–30%, while it ignites heterogeneously at <O₂> = 40–50%. In O₂/H₂O, biomass ignites homogeneously at <O₂> = 21–50%. With increasing oxygen concentration, the ignition delay time, volatile burnout time and char burnout time are decreased, and the volatile flame temperature and char combustion temperature are increased. At a certain oxygen concentration in both atmospheres, the ignition delay time, volatile burnout time and char burnout time of biomass are shorter than those of coal. Moreover, biomass has a higher volatile flame temperature but a lower char combustion temperature than coal. The ignition delay time, volatile burnout time and char burnout time in O₂/H₂O are lower than those in O₂/N₂ for coal and biomass. The presence of H₂O can improve the combustion rates of coal and biomass. The volatile flame shows a lower temperature in O₂/H₂O than in O₂/N₂ at <O₂> = 21–50%. The char combustion shows a lower temperature in O₂/H₂O than in O₂/N₂ at <O₂> = 21–30%, while this behavior is switched at <O₂> = 40–50%. The results contribute to the understanding of the ignition and combustion characteristics of coal and biomass in oxy-steam combustion.     

Effect of CO2 and steam gasification reactions on the oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, elevated levels of CO₂ and steam affect the heat capacity of the gas, radiant transport, and other gas transport properties. A topic of widespread speculation has concerned the effect of gasification reactions of coal char on the char burning rate. To asses the impact of these reactions on the oxy-fuel combustion of pulverized coal char, we computed the char consumption characteristics for a range of CO₂ and H₂O reaction rate coefficients for a 100 μm coal char particle reacting in environments of varying O₂, H₂O, and CO₂ concentrations using the kinetics code SKIPPY (Surface Kinetics in Porous Particles). Results indicate that gasification reactions reduce the char particle temperature significantly (because of the reaction endothermicity) and thereby reduce the rate of char oxidation and the radiant emission from burning char particles. However, the overall effect of the combined steam and CO₂ gasification reactions is to increase the carbon consumption rate by approximately 10% in typical oxy-fuel combustion environments. The gasification reactions have a greater influence on char combustion in oxygen-enriched environments, due to the higher char combustion temperature under these conditions. In addition, the gasification reactions have increasing influence as the gas temperature increases (for a given O₂ concentration) and as the particle size increases. Gasification reactions account for roughly 20% of the carbon consumption in low oxygen conditions, and for about 30% under oxygen-enriched conditions. An increase in the carbon consumption rate and a decrease in particle temperature are also evident under conventional air-blown combustion conditions when the gasification reactions are included in the model.     

Oxy-fuel combustion of pulverized coal: Characterization,fundamentals, stabilization and CFD modeling

Oxy-fuel combustion has generated significant interest since it was proposed as a carbon capture technology for newly built and retrofitted coal-fired power plants. Research, development and demonstration of oxy-fuel combustion technologies has been advancing in recent years; however, there are still fundamental issues and technological challenges that must be addressed before this technology can reach its full potential, especially in the areas of combustion in oxygen-carbon dioxide environments and potentially at elevated pressures. This paper presents a technical review of oxy-coal combustion covering the most recent experimental and simulation studies, and numerical models for sub-processes are also used to examine the differences between combustion in an oxidizing stream diluted by nitrogen and carbon dioxide. The evolution of this technology from its original inception for high temperature processes to its current form for carbon capture is introduced, followed by a discussion of various oxy-fuel systems proposed for carbon capture. Of all these oxy-fuel systems, recent research has primarily focused on atmospheric air-like oxy-fuel combustion in a CO₂-rich environment. Distinct heat and mass transfer, as well as reaction kinetics, have been reported in this environment because of the difference between the physical and chemical properties of CO₂ and N₂, which in turn changes the flame characteristics. By tracing the physical and chemical processes that coal particles experience during combustion, the characteristics of oxy-fuel combustion are reviewed in the context of heat and mass transfer, fuel delivery and injection, coal particle heating and moisture evaporation, devolatilization and ignition, char oxidation and gasification, as well as pollutants formation. Operation under elevated pressures has also been proposed for oxy-coal combustion systems in order to improve the overall energy efficiency. The potential impact of elevated pressures on oxy-fuel combustion is discussed when applicable. Narrower flammable regimes and lower laminar burning velocity under oxy-fuel combustion conditions may lead to new stability challenges in operating oxy-coal burners. Recent research on stabilization of oxy-fuel combustion is reviewed, and some guiding principles for retrofit are summarized. Distinct characteristics in oxy-coal combustion necessitate modifications of CFD sub-models because the approximations and assumptions for air-fuel combustion may no longer be valid. Advances in sub-models for turbulent flow, heat transfer and reactions in oxy-coal combustion simulations, and the results obtained using CFD are reviewed. Based on the review, research needs in this combustion technology are suggested.     

Rapid pyrolysis and CO2 gasification of anthracite at high temperature

Anthracite could be burnt efficiently at high temperature utilizing oxy-coal technology. To clarify the effects of temperature and atmosphere on char porosity characteristics, char morphology, fuel-N conversion, and reducing products release, rapid pyrolysis and CO₂ gasification of anthracite was carried out in a high temperature entrained-flow reactor to simulate the condition in a pulverized coal furnace. Developed pore structure was formed in the gasification chars, which could be contributed to charCO₂ reaction at high temperatures. More mesopores were formed in internal carbon skeleton and retained against collapse and coalescent for gasification chars than pyrolysis chars. Compared with pyrolysis char, smoother and denser surface was observed in gasification char with the irregular bulges disappeared due to the destruction of external carbon skeleton. Char-N could be oxidized to NO in CO₂ atmosphere and then reduced to N₂ by (CN) on the char surface. Char-N release was greatly promoted due to gasification reaction along with poly-condensation at high temperature; and the preact release of char-N would result in a larger portion of NO_x reduction in the following reduction zone with the oxygen-staging combustion technology compared with that in air-staging combustion. Complementally, homogeneous reduction in NO_x emission would play a minor effect for anthracite in oxy-coal combustion because of the deficiency of CH₄ and HCN, especially at high temperature.     

Nitric oxide emissions during the evolution of gasified char in the reduction layer during a grate-fired process

This work examined the effects of CO₂ gasification in the reduction layer on NO emissions during subsequent char combustion in the oxidation layer during a grate-fired process. In experimental trials, the pyrolysis char of Shenhua bituminous coal was initially gasified in CO₂, employing different conversion rates so as to vary the residence time of the char in the reduction layer. The pore structure and degree of graphitization of the char were monitored and the effects of CO₂ gasification on NO emissions were ascertained. In this manner, the relationship between the transformation of char nitrogen and the physicochemical characteristics of the char was clarified. The effects of CO₂ gasification on the properties of the char and NO emissions in the subsequent oxidation layer were determined. The results show that CO₂ gasification can improve the pore structure and degree of graphitization of the char, such that NO emissions are reduced in an inert atmosphere. However, the conversion rate of char nitrogen will increase in conjunction with oxidative combustion.     

Pyridine and pyrrole oxidation under oxy-fuel conditions

In this article, a study on pyridine and pyrrole oxidation under oxy-fuel conditions has been carried out. The experimental results indicate that when the temperature is above 800°C, concentration of N₂O in the offgas quickly destructs mainly into N₂ with the increase of temperature. Both NO and N₂O concentrations can be enlarged, obviously due to the increase of oxygen concentration. In addition, the effect of gas atmosphere on pyrrole oxidation is quite different from that on pyridine oxidation. Introduction of high content CO₂ in oxy-fuel combustion can lead to a certain migration change of fuel nitrogen.     

The fate of char-N at pulverized coal conditions

The fate of char-N (nitrogen removed from the coal matrix during char oxidation) has been widely studied at fluidized bed conditions. This work extends the study of char-N to pulverized coal conditions. Coal chars from five parent coals were prepared and burned in a laboratory-scale pulverized coal combustor in experiments designed to identify the parameters controlling the fate of char-N. The chars were burned with natural gas (to simulate volatiles combustion) in both air and in a nitrogen-free oxidant composed of Ar, CO₂, and O₂. In some experiments, the char flames were doped with various levels of NO or NH₃ to simulate formation of NO_x from volatile-N (nitrogen removed during coal devolatilization). The conversion of char-N to NO_x in chars burned in the nitrogen-free oxidant was 50-60% for lignites and 40-50% for bituminous coals. In char flames doped with NO_x, the apparent conversion of char-N to NO_x (computed using the NO_x measurements made before and after the addition of char to the system) decreased significantly as the level of NO_x doping increased. With 900 ppm NO_x present before the addition of char, apparent conversion of char-N to NO_x was close to 0% for most chars. While there is no clear correlation between nitrogen content of the char and char-N to NO_x conversion at any level of NO_x in the flame, the degree of char burnout within a given family of chars does play a role. Increasing the concentration of O₂ in the system in both air and nitrogen-free oxidant experiments increased the conversion of char-N to NO_x. The effects of temperature on NO_x emissions were different at low (0 ppm) and high (900 ppm) levels of NO_x present in the flame before char addition.     

The study of co-combustion characteristics of coal and microalgae by single particle combustion and TGA methods

The co-combustion characteristics of coal and microalgae with different blending ratios and under different atmospheres are studied by single particle combustion and thermogravimetric analysis methods. The combustion processes of coal, microalgae and their blends in the single particle combustion experiment have two stages, while the combustion process of coal in the thermogravimetric analysis experiment only has one stage. With the increasing blending ratio of microalgae, flames of volatiles and char of fuels become dimmer and smaller, and the average flame temperature decreases from about 1400 °C to about 1200 °C. The ignition delay time decreases from 200 ms to 140 ms, and the experimental ignition delay time of blended fuels is lower than the theoretical ignition delay time, which demonstrates that the synthetic effect between coal and microalgae exists. To analyze the influence of oxy-fuel atmosphere on the combustion characteristics, the air is replaced by the O₂/CO₂ atmosphere. The replacement decreases the luminosity, size and average temperature of flames. The average flame temperature of volatiles decreases from 1449.4 °C to 1151.2 °C, and that of char decreases from 1240.0 °C to 1213.4 °C. The replacement increases the ignition delay time of fuel from 80 ms to 100 ms. Increasing mole fraction of O₂ in O₂/CO₂ atmosphere can offset these influences. With the increasing mole fraction of O₂, flames of volatiles and char of fuels become brighter and larger, the average flame temperature increases from about 1100 °C to about 1300 °C, while the ignition delay time decreases from 100 ms to 77 ms.     

Oxidation mechanism of ammonia-N/coal-N during ammonia-coal co-combustion

Ammonia-coal co-combustion is a feasible approach to reduce CO₂ emissions during thermal power generation, it is necessary to study NO formation mechanism in ammonia-coal co-firing to realize low-carbon and low-nitrogen combustion. The experimental results showed that temperature and ammonia ratio have a significant effect on the NO formation. Under the same ammonia blending amount, the NO production increased first and then decreased with temperature increasing. Theoretical calculations revealed that the formation of NH in NH₃→NH→NO is one of the factors restricting ammonia combustion. NH oxidation on the char surface first occurred in the NH/coal/O₂ combustion system, and realized the conversion of N to NO, HNO and NO₂ through different reaction paths. Combined with the experimental and theoretical calculation results, it was concluded that the reduction of NO by ammonia/char is enhanced at high temperature (>1300 °C), which reduces the conversion of ammonia-N/coal-N to NO.     

The intrinsic reactivity of coal char conversion compared under different conditions of O2/CO2, O2/H2O and air atmospheres

The reasons for the intrinsic reactivity differences in coal char conversion under an O₂/H₂O atmosphere compared with that under an O₂/CO₂ or O₂/N₂ atmosphere have been investigated in a thermogravimetric analyzer by a simple variable activation energy (SVAE) method combined with an adsorption/desorption reaction mechanism. The results show that only CO₂ or H₂O chemisorption occurred in the non-isothermal experiments, not gasification; however, the intrinsic reaction rate (IRR) of coal char conversion at the same O₂ concentration still increases in an orderly manner under O₂/CO₂, O₂/N₂ and O₂/H₂O atmospheres. This result is due to the different chemisorption mechanisms of CO₂ and H₂O, namely, the production of C(CO), C(OH) and C(H) from CO₂ and H₂O chemisorption. At the same O₂ concentration, the trends and magnitudes of variable activation energies for coal char combustion under O₂/CO₂ and O₂/N₂ atmospheres are similar, while they are very different from those under O₂/H₂O conditions. Therefore, CO₂ has little influence on the reactivity, while H₂O changes the reactivity. In addition, according to the developed reaction mechanism, it is concluded that the SVAE method contributes to the characteristic intrinsic reactivity of coal char conversion under different atmospheres.     

Co-firing of Thai lignite and municipal solid waste (MSW) in a fluidised bed: Effect of MSW moisture content

Co-firing investigation of a high-moisture-content municipal solid waste (MSW) with Thai lignite have been performed in a laboratory-scale fluidised bed to study the effects of MSW moisture content on the combustion and emission characteristics of major gaseous pollutants. In this study the comparison of 35%- and 60%-moisture MSWs were tested. The results show that the bed temperature in the case of 35%-moisture content is higher than for in case of 60%-moisture content due to the difference of physical properties of the fuel. The combustion efficiency for the case of 35%-moisture MSW is higher than that for 60%-moisture MSW due to higher bed temperature at lower waste moisture content. The synergistic effect of the co-firing of lignite with MSW reduces the emission of CO leading to increase in combustion efficiency. CO concentration for the case of 35%-moisture content is generally lower, and is much less sensitive to the level of excess air. Both the concentration values of SO₂ and the fuel-S converted are lower for lower moisture content waste, particularly at high mass fraction of waste. The fuel mixture with low-moisture in waste gives higher fuel-N conversion to NO whereas the fuel-N conversion to N₂O is higher for higher moisture content waste, particularly at high excess air.     

Single particle ignition and combustion of anthracite,semi-anthracite and bituminous coals in air and simulated oxy-fuel conditions

A fundamental investigation has been conducted on the combustion behavior of single particles (75–150 μm) of four coals of different ranks: anthracite, semi-anthracite, medium-volatile bituminous and high-volatile bituminous. A laboratory-scale transparent laminar-flow drop-tube furnace, electrically-heated to 1400 K, was used to burn the coals. The experiments were performed in different combustion atmospheres: air (21%O₂/79%N₂) and four simulated dry oxy-fuel conditions: 21%O₂/79%CO₂, 30%O₂/70%CO₂, 35%O₂/65%CO₂ and 50%O₂/50%CO₂. The ignition and combustion of single particles was observed by means of three-color pyrometry and high-speed high-resolution cinematography to obtain temperature–time histories and record combustion behaviors. On the basis of the observations made with these techniques, a comprehensive examination of the ignition and combustion behaviors of these fuels was achieved. Higher rank coals (anthracite and semi-anthracite) ignited heterogeneously on the particle surface, whereas the bituminous coal particles ignited homogeneously in the gas phase. Moreover, deduced ignition temperatures increased with increasing coal rank and decreased with increasing oxygen concentrations. Strikingly disparate combustion behaviors were observed depending on the coal rank. The combustion of bituminous coal particles took place in two phases. First, volatiles evolved, ignited and burned in luminous enveloping flames. Upon extinction of these flames, the char residues ignited and burned. In contrast, the higher rank coal particles ignited and burned heterogeneously. The replacement of the background N₂ gas of air with CO₂ (i.e., changing from air to an oxy-fuel atmosphere) at the same oxygen mole fraction impaired the intensity of combustion. It reduced the combustion temperatures and lengthened the burnout times of the particles. Increasing the oxygen mole fraction in CO₂ to 30–35% restored the intensity of combustion to that of air for all the coals studied. Volatile flame burnout times increased linearly with the volatile matter content in the coal in both air and all oxygen mole fractions in CO₂. On the other hand, char burnout times increased linearly or quadratically versus carbon content in the coal, depending on the oxygen mole fraction in the background gas.     

Combustion behavior of single particles from three different coal ranks and from sugar cane bagasse in O2/N2 and O2/CO2 atmospheres

The combustion behavior of single fuel particles was assessed in O₂/N₂ and O₂/CO₂ background gases, with oxygen mole fractions in the range of 20–100%. Fuels included four pulverized coals from different ranks (a high-volatile bituminous, a sub-bituminous and two lignites) as well as pulverized sugarcane-bagasse, a biomass residue. Particles of 75–90 μm were injected under laminar flow in a bench-scale, transparent drop-tube furnace (DTF), electrically-heated to 1400 K where, upon experiencing high heating rates, they ignited and burned. The combustion of individual particles was observed with three-color optical pyrometry and high-speed high-resolution cinematography to obtain temperature and burnout time histories. Based on combined observations from these techniques, a comprehensive understanding of the behaviors of these fuels was developed under a variety of conditions, including simulated oxy-fuel combustion. The fuels exhibited distinct combustion behaviors. In air, the bituminous coal particles burned in two distinctive modes; the volatiles burned in bright envelope flames surrounding the devolatilizing char particles followed by heterogeneous char combustion. The volatile matter of sub-bituminous coal particles burned either in subdued envelope flames, surrounding devolatilizing and occasionally fragmenting chars, or heterogeneously at the char surface. Lignite particles typically burned with extensive fragmentation, and their volatiles burned simultaneously with the char fragments. The volatiles of bagasse particles burned in spherical and transparent envelope flames. Increasing the oxygen mole fraction in N₂, increased flame and char surface temperatures, and decreased burnout times; particles of all fuels burned more intensely with an increasing tendency of the volatiles to burn closer to the char surface. When the background gas N₂ was substituted with CO₂, the combustion of all fuels was distinctly less intense; at moderate O₂ mole fractions (<30%) most particles did not ignite under active flow conditions in the furnace (they did ignite under quiescent gas flow conditions in the DTF). Increasing the oxygen mole fraction in CO₂ increased the likelihood of combustion and its intensity. Combustion of volatiles in envelope flames was suppressed in the presence of CO₂, particularly under active gas flow in the DTF.     

Experimental study on effects of combustion atmosphere and coal char on NO2 reduction under oxy-fuel condition

Nitrogen oxides (NO_x) as the principal air pollutants are mainly from the combustion of fossil fuels. Oxy-fuel combustion is a promising clean coal technology, by which carbon dioxide (CO₂) can be captured in large-scale and NO_x emission can be reduced significantly. The formation of nitrogen dioxide (NO₂) in oxy-fuel combustion exceeds that under traditional air condition. However, the specific studies on NO₂ chemistry under oxy-fuel condition are still insufficient and the functional mechanisms of minerals and combustion atmosphere on NO₂ reduction have yet to be fully understood. The objective of present study is to experimentally clarify the effects of combustion atmosphere and coal char on NO₂ reduction in oxy-fuel combustion using a fixed-bed reactor. Experimental results showed that the decomposition of NO₂ had a strong temperature dependence and the NO₂ reduction rate showed a positive variation with temperature. The strength of catalytic activity in NO₂ reduction to nitric oxide (NO) was Fe₂O₃ > MgO > CaO > Al₂O₃ > Na₂CO₃ > K₂CO₃ > SiO₂. In addition, the increased concentrations of carbon monoxide (CO) and CO₂ could promote the reduction of NO₂, while the low content of CO₂ only established a slight impact on NO₂ reduction. However, the increase of oxygen (O₂) concentration displayed an inhibition effect on NO₂ reduction to a certain extent. The variation of atmosphere in oxy-fuel combustion generated a substantial influence on the creation and reduction of NO₂. The char prepared in lower temperature exhibited a higher promotion effect on the consumption of NO₂. Higher contents of fixed carbon and basic oxides had more obvious stimulation effects on NO₂ reduction. Fixed carbon had a superior activity in NO₂ reduction than ash. The kinetic analysis indicated that high content of CO and the presence of char could reduce the apparent activation energy of NO₂ reduction. The present study can be helpful to improve the understanding of NO₂ chemistry in oxy-fuel combustion.     

Char nitrogen conversion: implications to emissions from coal-fired utility boilers

The contribution of nitrogen present in the char on the production of nitrogen oxides during char combustion was analyzed. A literature review summarizes the current understanding of the mechanisms that account for the formation of NO and N₂O from the nitrogen present in char. The review focused on: (1) the functionalities in which nitrogen is present in the coal and how they evolve during coal devolatilization; (2) the mechanism of nitrogen release from the char to the homogeneous phase and its further oxidation to NO; and (3) the reduction of NO on the surface of the char. The critical analysis of these three issues allowed identification of uncertainties and well-founded conclusions observed in the literature for this system.

The existing models for the production of nitrogen oxides from char-N were also reviewed. A critical analysis of the assumptions made in these models and how they affect the final predictions is presented. Finally, a simplified version of these models was used to perform a parametric analysis evaluating the impact of several parameters on the total conversion of char-N to NO. These parameters include: (1) the rate of NO reduction on the char surface; (2) the rate of carbon oxidation; and (3) early vs. late nitrogen release during the char oxidation process. The results underscore the importance of the reaction of NO reduction on the char surface to the final conversion of char-N to NO.