Modelling of NO and N2O emissions from biomass-fired circulating fluidized bed combustors

A model for NO and N₂O emissions from biomass-fired circulating fluidized bed (CFB) combustors has been developed and evaluated in this study. All the model parameters were chosen for a typical woody biomass-pinewood chips. Both drying and devolatilization of biomass particles were modelled with limited rates, which were selected from the literature based on woody biomass fuels. The partition of fuel-nitrogen between volatiles and char was also specifically chosen for pinewood based on available experimental data from the literature. Volatile nitrogen was assumed to consist of NH₃, HCN and N₂ with the distribution between three species as input parameters to the model. Twenty-five homogenous and heterogeneous global chemical reactions were included in the model, of which 20 reactions represents the global fuel-nitrogen reactions. Both gaseous and solid phase were assumed to be in plug flow. The model has been applied to the modelling of a 12 MW_th CFB boiler. The predicted N₂O emissions were always less than 5 ppmv for pinewood combustion, which was consistent with the experimental results. The predicted NO emissions increased with the total excess air of the riser and the fuel-N content while the predicted percentage conversion of fuel-N to NO decreased with increasing fuel-N content. The NO emissions were also predicted to decrease with increasing primary zone stoichiometry. These predictions agree with the experimental results. The predicted NO emissions decreased slightly with increasing bed temperature, whereas experiments showed that NO emissions slightly increased with bed temperature for birch chips combustion and did not change with bed temperature for fir chips combustion. Sensitivity analyses reveal that the reaction between NO and char is the key reaction to determine the NO emissions.     

Effect of Operating Conditions on NOx and CO Emissions in a Pilot‐Scale Vortexing Fluidized‐Bed Combustor with Flue Gas Recirculation

In order to study the effect of flue gas recirculation (FGR) by primary air mixed with FGR or nitrogen on NO_x emissions in a fixed total primary air flow rate, the bed temperature, stoichiometric oxygen ratio in the combustion chamber, and excess oxygen ratio were investigated in a pilot‐scale vortexing fluidized‐bed combustor (VFBC). As a result, the NO_x emissions could effectively be decreased with FGR in the VFBC. The lower NO_x emissions were attributed to the fact that the FGR allows NO_x to enter the reactor again with the chance of being reduced and that the FGR contains more CO₂ to suppress NO_x formation or promote NO_x reduction through its conversion to CO by reaction with char.     

Experimental trends of NO in circulating fluidized bed combustion

Experimental trends for the dependence of CO, NO and N₂O emissions on bed temperature and oxygen concentration in circulating fluidized bed combustion (CFB) are presented. The main focus is on the nitrogen emission formation in the lower furnace area. A test campaign including seven tests with a laboratory scale CFB test rig were carried out to produce appropriate data of the phenomena. These experiments show that NO emissions above the dense bed decrease with decreasing temperature or oxygen concentration. Instead, N₂O emissions increase when the bed temperature is decreased and decrease when the oxygen concentration is decreased. These trends can partly be explained by heterogeneous reactions between NO and char, since decrease in temperature or oxygen concentration increases the bed char inventory. However, oxygen and temperature also affect directly on NO emissions. Correlations for the CO, NO, N₂O, NH₃ and HCN concentrations at the exit of dense bed were developed. This type of correlations can, among other things, be applied as boundary conditions to the more sophisticated CFD models that are usually applied to modelling of diluted part of the furnace. CFD modelling of the dense bed area is complicated and accuracy is not sufficient, thus simplified experimental correlations can aid in the development of furnace design towards better emission performance.     

Combustion gas and NO emission characteristics of hazardous waste mixture particles in a fixed bed

Experiments with fixed-bed incinerators were carried out to model the combustion characteristics and gas emission characteristics of hazardous waste mixture particles in a grate furnace. The results indicate that combustion can be divided into three stages: ignition, main combustion and combustion completion stage. According to the various concentrations of O₂, CO₂ and CO, the main combustion stage can be subdivided into pyrolysis gas combustion and char combustion. Primary air rate, moisture and particle size have significant effects on concentrations of combustion gases and NO. Bed height has no effect on CO₂ concentrations but does have an effect on other combustion gases and NO emissions.     

Experimental study of NO reduction over biomass char

Some biomass fuels produce more NO_x than coal on the basis of heating value, giving rise to the necessity and importance of controlling NO_x emission in biomass combustion. The present study investigated the NO reduction over biomass char in a fixed bed quartz reactor in the temperature range of 973–1173 K. The reaction rates of three biomass chars (sawdust, rice husk and corn straw) with NO were compared with Datong bituminous coal char. The results show that the reaction orders of biomass chars for NO are of fractional order and independent of temperature. Biomass chars are more active in reducing NO than coal char. The characteristics of biomass char affect NO conversion. Biomass char formed at high pyrolysis temperature, especially large in particle size, is less active in reducing NO. To some extent, increase of reaction temperature and char loading enhance NO conversion. There exists an optimum bed height for the highest NO conversion. Moreover, NO reduction over biomass char is also enhanced in the presence of CO, O₂ and SO₂.     

Formation and reduction of nitric oxide in fixed-bed combustion of straw

Mechanisms of nitric oxide (NO) formation and reduction in fixed-bed combustion of straw have been modeled mathematically and verified experimentally. The model for the straw combustion and nitrogen chemistry consists of sub-models for evaporation, pyrolysis, tar and char combustion, nitrogen conversion, and energy and mass conservation. Twenty chemical reactions are included, of which 12 belong to the fuel nitrogen reaction network. Volatile nitrogen is assumed to be NO, NH₃, HCN and HNCO, and char nitrogen is converted to NO during char oxidation. The model predictions are in qualitative agreement with the measurements during the ignition phase, i.e. when the combustion front passes through the un-burnt fuel. The yield of NO can be reduced considerably by using a low primary air flow due to the longer gas residence in the fixed-bed, while the NO exhaust concentration is insensitive to the bed temperature. The NO exhaust concentration initially reaches a maximum and then decreases towards a stable value after the straw bed is ignited. Variations of NO, NH₃, HCN, and HNCO concentrations in the ignition flame front indicate that a large quantity of NO can be reduced in the thin flame front zone. The developed model is further validated by separate experiments in which NO or NH₃ was added at the middle through tubes or at the bottom of the bed with the primary air flow. Both the simulations and measurements showed that the variation of the NO exhaust concentration is small as compared with the injected NO or NH₃ concentration. According to the simulations and experiments, it is proposed that flue gas recirculation may be a very effective method of reducing NO emissions from flue gas in the fixed-bed combustion of straw. Calculations indicated that about 20% of the flue gas may be recirculated without significantly affecting the combustion behavior.     

无烟煤化学链燃烧过程燃料氮转化释放特性

基于赤铁矿石载氧体,在小型单流化床反应器上,开展煤挥发分和焦炭的化学链燃烧研究,探讨挥发分氮和焦氮在化学链燃烧过程中的转化特性。研究表明:燃料氮释放的中间产物HCN和NH₃与铁矿石载氧体具有较高的化学反应亲和性,易于被载氧体氧化生成N₂和NO。淮北无烟煤挥发分氮转化过程中,NO是唯一的氮氧化物,反应器出口中间产物NH₃的释放份额略高于HCN。在煤焦化学链燃烧还原过程中,部分燃料氮释放的中间产物HCN和NH₃被铁矿石氧化导致少量NO的生成,还原过程中无N₂O的释放;较高的还原反应温度加速了NO的生成。减少进入载氧体氧化再生过程的焦炭量可减少空气反应器NO和N₂O的生成。     

Effects of operation parameters on NO emission in an oxy-fired CFB combustor

Oxy-fuel Circulating Fluidized Bed (CFB) combustion technology, a very promising technology for CO₂ capture, combines many advantages of oxy-fuel and CFB technologies. Experiments were carried out in a 50 kW_th CFB facility to investigate how operation parameters influence the NO emission in O₂/CO₂ atmospheres. The simulated O₂/CO₂ atmospheres were used without recycling the flue gas. Results show that NO emission in 21% O₂/79% CO₂ atmosphere is lower than that in air atmosphere because of lower temperature and higher char and CO concentrations in the dense bed. Elevating O₂ concentration from 21% to 40% in O₂/CO₂ atmosphere enhances fuel-N conversion to NO. Increasing bed temperature or oxygen/fuel stoichiometric ratio brings higher NO emission in O₂/CO₂ atmosphere, which is consistent with the results in air-fired CFB combustion. As primary stream fraction increases, NO emission increases more rapidly in O₂/CO₂ atmosphere than that in air atmosphere. Stream staging is more efficient for controlling NO emission in oxy-CFB combustion than that in air combustion. Oxygen staging provides an efficient way to reduce NO emission in oxy-CFB combustion without influencing the hydrodynamic characteristic in the riser.     

Catalytic effect of biomass ash on CO, CH4 and HCN oxidation under fluidised bed combustor conditions

In fluidised bed combustion heterogeneous reactions catalysed by the bed material, CaO, and char are significant for the emission levels for instance of NO, N₂O, and CO. The catalysts present in the bed affect significantly the selectivity of HCN and NH₃ oxidation, which are known as precursors of NO_x (i.e. NO and NO₂) and N₂O emissions from solid fuel combustion. Thus the catalytic activity of biomass ashes may also be responsible for the negligible N₂O emissions from biomass combustion due to the presence of a large amount of solids in fluidised bed combustion, homogeneous oxidation may be suppressed within the bed by the quenching of the radicals. For this reason the catalytic oxidation of hydrocarbons and CO on the bed material may be of significance for the total burnout within the fluidised bed combustor.Within this study the effect of different ashes from spruce wood, peat, and for comparison bituminous coal on the oxidation of CH₄, CO, and HCN was studied. The different ashes were shown to have a strong catalytic activity for the oxidation of CH₄, CO, and HCN. In HCN oxidation the selectivity towards NO is high, whereas very little N₂O is formed. The activity of the ashes is strongly dependent on the fuel, which may be explained by their composition.The kinetics of the oxidation of CO and HCN in the temperature range relevant for fluidised bed combustion, i.e. 800-900 °C, has been evaluated for spruce wood ash.     

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.     

Releases of NO and its precursors from coal combustion in a fixed bed

Experiments have been carried out to investigate the emissions of nitrogen species including NO and its precursors during temperature-programmed coal combustion by TG/EGA method. Experimental results show that the conversion ratio of fuel nitrogen to NO is the highest, followed by that of fuel nitrogen to HCN and the conversion ratio to NH₃ is negligibly small. Nitrogen is retained in the char and released mainly as NO at the later stages of coal combustion. HCN and NO are both primary products from coal char oxidation. Coal rank, heating rate, indigenous minerals and external additives are the major influential factors of the nitrogen species release. Higher rank coals with higher fuel ratio have higher NO releases. HCN release decreases as fuel ratio increases for most coals. The fuel nitrogen conversion to NO increases and the fuel nitrogen conversion to HCN decreases with the increase of heating rate, which may imply that the char nitrogen prefers to react with oxygen to form NO instead of HCN while coal char is combusted at higher temperatures. Different metallic additives show different effects on nitrogen species emission and the effects of indigenous minerals on nitrogen release can be qualitatively estimated by ash analyses.     

Influence of mineral matter in coal on decomposition of NO over coal chars and emission of NO during char combustion

NO-char reaction and char combustion in the presence and absence of mineral matter were studied in a quartz fixed bed reactor. Eight chars were prepared in a fluidized bed at 950 °C from four Chinese coals that were directly carbonized without pretreatment or were first deashed before carbonization. The decomposition of NO over these coal-derived chars was studied in Ar, CO/Ar and O₂/Ar atmospheres, respectively. The results show that NO is more easily reduced on chars from the raw coals than on their corresponding deashed coal chars. Mineral matter affects the enhancement both of CO and O₂ on the reduction of NO over coal chars. Alkali metal Na in mineral matter remarkably catalyzes NO-char reaction, while Fe promotes NO reduction with CO significantly. The effect of mineral matter on the emission of NO during char combustion was also investigated. The results show that the mineral constituents with catalytic activities for NO-char reaction result in the decrease of NO emission, whereas mineral constituents without catalytic activities lead to the increase of NO emission. Correlation between the effects of mineral matter on NO-char reaction and NO emission during char combustion was also discussed.     

城市污泥流化床燃烧过程中气态污染物排放特性

在6kW_th鼓泡流化床实验台上进行了城市污泥的燃烧实验,研究了烟气再循环气氛和空气气氛下燃烧温度、过量氧气系数、二次风比率对气态污染物排放特性的影响。研究结果表明：燃烧温度升高,NO排放浓度明显升高,SO₂排放浓度亦呈上升趋势;过量氧气系数提高,NO排放浓度呈显著上升趋势,SO₂排放浓度则呈下降趋势;增大二次风比率,NO排放浓度呈现先降低后升高的趋势,但总体减排效果并不明显,SO₂排放浓度出现少量增长;烟气再循环工况下,NO排放浓度随燃烧温度和过量氧气系数变化的趋势与空气气氛燃烧时一致;烟气再循环率从0增加至1,NO排放浓度明显下降;烟气再循环率达到较高值后,NO排放浓度随之提高而降低的趋势减弱;烟气再循环率逐渐升高过程的前期,烟气中CO浓度出现显著升高;再循环率超过0.3后,CO浓度在一定范围内波动,不再升高。     

Combustion and air emissions from co‐firing a wood biomass,a Canadian peat and a Canadian lignite coal in a bubbling fluidised bed combustor

The effects of particle size, fuel blending ratio, moisture content and excess air ratio on combustion efficiency and air emissions (CO₂, CO, SO₂ and NO_x) from the co‐combustion of white pine or peat with a Canadian lignite coal, were examined in a pilot‐scale bubbling fluidised bed combustor. Pelletising was important for the efficient combustion of wood due to its high volatile content. Co‐firing lignite and pine pellets gave a proportional reduction in SO₂ and NO_x emissions with blending ratio, while co‐firing of peat and lignite resulted in increased SO₂ emissions, but decreased NO_x emissions. Moisture promotes combustion but with increased CO emissions, and results in increased NO_x emissions, and decreased SO₂ emissions. High excess air decreased CO, but moderately increased SO₂ and NO_x emissions. © 2011 Canadian Society for Chemical Engineering     

The application of FLOX/COSTAIR technologies to reduce NOx emissions from coal/biomass fired power plant: A technical assessment based on computational simulation

Nitrogen oxides (NO_x) is one of the harmful emissions from power plants. Efforts are made to reduce NO_x emissions by researchers and engineers all the times. NO_x emissions are from three resources during the combustion: prompt NO, fuel NO and thermal NO. The last one - thermal NO, which is described by ‘Zeldovich-mechanism’, is the main source for NO_x emissions. The thermal NO emission mainly results from the high combustion temperature in the combustion process. In order to control the NO formation, the control of peak combustion temperature is the key factor, as well as the oxygen concentration in the combustion areas. Flameless oxidation (FLOX) and continuous staged air combustion (COSTAIR) are two relatively new technologies to control the combustion temperature and the reaction rate and consequently to control the NO_x emissions.In this study both FLOX and COSTAIR technologies are assessed based on a 12 MW_e, coal-fired, circulating fluidised bed combustion (CFBC) power plant by using ECLIPSE simulation software, together with a circulating fluidised bed gasification (CFBG) plus normal burner plant. Two different fuels - coal and biomass (straw) are used for the simulation. The technical results from the study show that the application of FLOX technology to the plant may reduce NO_x emissions by 90% and the application of COSTAIR technology can reduce NO_x emissions by 80-85% from the power plant. The emissions from the straw-fuelled plants are all lower than that of coal-fuelled ones although with less plant efficiencies.     

Boundary layer model for char combustion and gasification

A non-steady boundary layer model is developed for numerical simulation of combustion and gasification of a single shrinking char particle. The model considers mass and energy conservation coupled with heterogeneous char reactions producing CO and homogeneous oxidation of CO to CO₂ in the boundary layer surrounding the char particle. Mass conservation includes accumulation, molecular diffusion, Stefan flow and generation by chemical reaction. Energy conservation includes radiation transfer at the particle surface and heat accumulation within the particle. Simulation results predict experimentally measured conversion and temperature profiles of a burning Spherocarb particle in a laminar flow reactor. Effects of bulk oxygen concentration and particle size on the combustion process are addressed. Predicted particle temperature is significantly affected by boundary layer combustion of CO to CO₂. With increasing particle size, char gasification to char combustion ratio increases, resulting in decreasing particle temperature and increasing peak boundary layer temperature.     

In-bed char combustion of Australian coals in PFBC. 2. Char combustion without secondary fragmentation

Char combustion parameters that significantly affect the in-bed combustion of char in PFBC were determined experimentally using a batch-fed PFBC. The ratio of carbon to oxygen consumed on the surface of a burning char particle was determined and it was concluded that CO was the only product of char combustion in PFBC.

Model simulations revealed that, for PFBC, mass transfer controlled the combustion of large char particles ≥2 mm, whereas the combustion of small char particles below 0.9–2 mm was controlled by both mass transfer and chemical kinetics.

System pressure influenced the char combustion via the interaction between chemical kinetics and the mass transfer of oxygen to the char. Char particle temperature varied markedly with oxygen partial pressure in the particulate phase, indicating a distribution of char particle combustion rates in PFBC. In modelling char combustion in PFBC, the temperature of char particles in the bed should be calculated at different locations based on a heat balance around the burning char particle taking into account the local bed oxygen concentration.     

海藻生物质颗粒流化床燃烧试验研究

在小型流化床试验台上研究了海藻颗粒(条浒苔与马尾藻)的流化床燃烧。海藻在流化床内的挥发分析出燃烧时间都在1 min左右。条浒苔颗粒在流化床中燃烧先进行脱水和挥发分的燃烧,接着发生焦炭燃烧,其燃烧过程符合缩核模型,炭核由外向内逐层燃烧,而灰层半径几乎不变。但马尾藻颗粒由于挥发分的大量快速释放而迅速膨胀破碎成屑。另外通过对条浒苔颗粒及不同燃烧时间后收集的焦炭颗粒剖面的SEM扫描电镜观察,发现随着燃烧的进行,颗粒内孔隙增大,微孔表面粗糙。进一步详细研究了两种海藻颗粒(条浒苔与马尾藻)在流化床内单次投料下的燃烧。随着床温的升高,条浒苔释放NO_x相对浓度增加,CO相对浓度减少。而马尾藻释放气体中SO₂与NO_x含量相对条浒苔有所增加;随着床温的升高,CO相对浓度减少。床温的升高使得床内传热速率加快,两种海藻挥发分的析出提前,燃尽时间缩短。风速、床高的升高使得两种海藻燃烧容易,燃尽时间缩短。     

Modelling of CO2, CO, SO2, O2 and NOx emissions from the oxy-fuel combustion in a circulating fluidized bed

The paper presents a model of coal combustion in air and oxygen-enriched CFB environment. A computer program to calculate the CO₂, CO, SO₂, NO_x and O₂ emissions from the combustion of solid fuels in a circulating fluidized bed boiler was created. The validity of this program was verified by measurements on a 0.1MW_th OxyFuel-CFB Test Rig.The calculations have been carried out for air and so-called oxy-fuel conditions, i.e. when combustion runs in a gas mixture based on O₂ and N₂, with various fractions of oxygen.The comparison between measured and predicted by model CO, SO₂, NO_x and O₂ emissions is shown in this paper. The results of the calculation showed, that the kinetic equations of some reaction have to be modified. Authors propose to use the reaction surface area instead of the specific internal surface area of char in rate constant formulas as the combustion nature changes from internal-kinetic to external-diffusion controlling regime.     

N2O emissions from fluidised bed combustion. The effect of fuel characteristics and operating conditions☆

Fluidised bed combustion (FBC) is a versatile and relative clean technology except with respect to nitrous oxide (N₂O) emissions. The emissions of N₂O from FBCs are very dependent on a number of operating conditions (temperature, sorbent addition, excess oxygen, etc.), fuel characteristics and many homogeneous and heterogeneous reactions that take place.This paper describes the results obtained during the study of the effect of coal type on N₂O emissions from FBC. The combustion tests were performed in a circulating fluidised bed pilot plant, using two coals: a Spanish subbituminous (Puertollano) and a bituminous coal from Colombia (Carbocol). Using supporting laboratory-scale fluidised bed pyrolysis experimental data with these fuels the partitioning of fuel-N and the formation of the most important N₂O precursors, NH₃, HCN and char was followed. The pyrolysis tests results showed that the major part of the nitrogen remained in the char. Both coals a produced similar amount of HCN, but the amount of char-N was lower with Carbocol coal that with Puertollano coal. The combustion results showed that the conversion of fuel-N to N₂O was higher on the tests with Puertollano coal than with Carbocol coal. For this it was concluded that the formation of N₂O via char-N oxidation was the most important pathway. The temperature profile of the combustor and the sorbent addition strongly influence N₂O emissions.