Experimental investigation of NOx emissions in oxycoal combustion

This work presents the results of an experimental investigation on NO_x emissions from coal combustion in a pilot scale test facility. Three oxidiser atmospheres have been compared, namely air, CO₂/O₂, and O₂ enriched recirculated flue gas. NO_x emissions from two different combustion modes have been studied, swirl flame and flameless combustion. The influence of the burner oxygen ratio and the oxidiser O₂ concentration on NO_x formation and reduction have been analysed. With increasing burner oxygen ratio, an increase of NO_x emissions has been obtained for air and CO₂/O₂ in both, swirl flame and flameless combustion. In case of the swirl flame, flue gas recirculation leads to a reduction of NO_x emissions up to 50%, whereas in case of flameless combustion this reduction is around 40% compared to CO₂/O₂. No significant impact of the oxidiser O₂ concentration in the CO₂/O₂ mixture on NO_x emissions is observed in the range between 18 and 27 vol.% in swirl flames. An analysis of NO_x formation and reduction mechanisms showed, that the observed reduction of NO_x emissions by flue gas recirculation cannot be attributed to the reduction of recirculated NO_x alone, but also to a reduced conversion of fuel-N to NO.     

Impact of air staging along furnace height on NOx emissions from pulverized coal combustion

Experiments were carried out on an electrically heated multi-path air inlet one-dimensional furnace to assess NO_x emission characteristics of an overall air-staged (also termed air staging along furnace height) combustion of bituminous coal. The impact of main parameters of overall air-staged combustion technology, including burnout air position, air stoichiometric ratio, levels of burnout air (the number of burnout air arranged at different heights of the furnace), and the ratios of the burnout air flow rates and pulverized coal fineness of industrial interest, on NO_x emission were simulated to study in the experimental furnace, as well as the impact of air staging on the carbon content of the fly ash produced. These results suggest that air-staged combustion affects a pronounced reduction in NO_x emissions from the combustion of bituminous coal. The more deeply the air is staged, the further the NO_x emission is reduced. Two-level air staging yields a greater reduction in NO_x emission than single-level air staging. For pulverized coal of differing fineness, the best ratio between the burnout air rates in the two-level staging ranges from 0.6 to 0.3. In middle air-staged degree combustion with f_M = 0.75, pulverized coal fineness, R₉₀ (%), has a greater influence on NO_x emission, whereas R₉₀ has little influence on NO_x emission for deep air-staged degree with f_M = 0.61. Air-staged combustion with proper burnout air position has little effect on the burnout. For overall air-staged combustion, proper burnout air position and air-staged rate should be considered together in order to achieve high combustion efficiency.     

Pulverized coal combustion and NOx emissions in high temperature air from circulating fluidized bed

A new technique of achieving high temperature air was adopted by combustion in high excess air ratio in a circulating fluidized bed (CFB). Experiments on pulverized coal combustion in high temperature air from the CFB were made in a down-fired combustor with the diameter of 220 mm and the height of 3000 mm. High temperature air with lower oxygen concentrations can be achieved steadily and continuously by combustion in the circulating fluidized bed. Pulverized coal combustion in high temperature air shows a uniform temperature profile along the axis of the down-fired combustor and the combustion efficiency is 99.8%. The NO_x emission is 390 mg/m³, 13% lower than the regulation for thermal power plants in China. The HCN and NH₃ emissions, as well as N₂O, are about zero in the exhaust.     

A reduced NOx reaction model for pulverized coal combustion under fuel-rich conditions

A reduced NO_x reaction model was developed for analysis of industrial pulverized coal firing boilers. The model was developed from experiments of laminar premixed combustion under a variety of stoichiometric ratios, burning temperatures, coal ranks (from sub-bituminous coal to anthracite) and particle diameters. Calculations agreed with experimental results for NO_x and nitrogen species (NH₃ and HCN), if the model assumed that the hydrocarbon radicals were formed not only from pyrolysis of volatile matter, but also from char oxidation and gasification. The presence of hydrogen in char at the final burnout stage supported this assumption. NO_x reduction by hydrocarbon radicals was the most important reaction in high temperature (>1500 K), fuel-rich, char combustion regions. NO_x reduction from nitrogen species was sensitive to peak NO_x concentration in volatile combustion regions, but NO_x emission downstream had little influence from the peak NO_x concentration. The heterogeneous reaction between char and NO_x was important for fuel-lean or low-temperature conditions.     

Coal characterisation for NOx prediction in air-staged combustion of pulverised coals

A series of world-traded coal samples has been tested using the Imperial College high temperature wire mesh apparatus (HTWM) in order to assess the relationship between high temperature (1600°C) char nitrogen content and NO_x formation in Hemweg Power Station (in the Netherlands) using deep furnace air staging. A linear relationship between high temperature char nitrogen and NO_x formation has been confirmed. These results suggest that high temperature char N content is the main factor limiting NO_x emissions with deep air-staged combustion.Char N and (hence apparently deep air-staged NO_x) can be predicted with an accuracy of approximately ±20% for most coals from the coal proximate and ultimate analysis—but this might not be sufficient for stations operating close to their emission limits. Measuring high temperature char N directly reduces the likely uncertainty in deep air-staged NO_x emissions for coals (and most blends) to approximately ±10%. Its use should be considered on a routine basis for coal selection on plants employing this technology.     

Simultaneous reduction of NOx and SO2 emissions from coal combustion by calcium magnesium acetate

The potential of calcium magnesium acetate (CMA) as a medium for the simultaneous control of NO_x and SO_x emissions has been investigated using a pulverized coal combustion rig operating at 80 kW. A US and a UK coal of significantly different sulphur contents were used as primary fuel and CMA was injected in solution form into the combustion gases by horizontally opposed twin-fluid atomisers at temperatures of 1100-1200 °C. SO₂ reductions typically greater than 80 and 70% were found for initial SO₂ levels of 1000 and 1500 ppm, respectively, at Ca/S ratios greater than 2.5. There did not appear to be significant limitation on sulphation by pore blockage using CMA due to the open structure formed during calcination and there is clear potential for zero SO₂ emissions at higher Ca/S ratios. The Ca content of the CMA in the form of CaO, via a droplet drying/particle calcination process, absorbs SO₂ by sulphation processes by penetration into the open pore structure of these particles. The effect of primary zone stoichiometry (λ₁=1.05, 1.15 and 1.4) on NO_x reduction was investigated for a range of CMA feed rates up to a coal equivalent of 24% of the total thermal input. NO_x reductions of 80, 50 and 30% were achieved at a primary zone stoichiometry of λ₁=1.05, 1.15 and 1.4, respectively, for a reburn zone residence time of 0.8 s. At lower equivalent reburn fuel fractions, coal gave greater NO_x reductions than CMA but similar levels were achieved above Rff=18%. The mechanism for NO_x reduction involves the organic fraction of CMA which pyrolyses into hydrocarbon fragments (CH_i), but to a lesser degree than coal, which may then react with NO_x in a manner similar to a conventional ‘reburn’ mechanism where NO_x is partly converted to N₂ depending on the availability of oxygen.     

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.     

Modelling of NOx adsorption over NOx adsorbers

Modelling of the phenomena involved during the adsorption of NO_x on NO_x trap catalysts was developed. The aim of the model is the prediction of the quantity of stocked barium nitrate as well as the emissions of NO and NO₂, as a function of time and temperature. The mechanism of the process is sounded on the adsorption of gas species (NO, NO₂, O₂) on platinum sites, equilibrium reaction between adsorbed species followed by the formation of Ba(NO₃)₂. This formation of barium nitrate is limited by the thermal decomposition reaction which liberates NO in the gas phase. The kinetic constant of decomposition of barium nitrate was determined by temperature programmed thermogravimetry on pure Ba(NO₃)₂, using the method of Freeman and Carroll. Other kinetic constants bound to the mechanism were estimated by fitting the results of the model to experimental results.The mechanism was validated for various values of the molar fraction of O₂, the molar fraction of NO and various values of the NO/NO₂ ratio in the gas entering the reactor. It was also tested with different catalyst compositions (variation of the platinum and BaO concentrations). The importance of oxygen in the process was clearly demonstrated as well as the promoting role of NO₂.     

Coal combustion modelling of large power plant, for NOx abatement

This paper presents the comparison of experimental results and computational fluid dynamics (CFD) simulations for a 600 MWe industrial pulverised coal power station. The power station measurements were made in a normal combustion mode and in an overfire air (OFA) mode. The agreement between the model and the data collected in the chimney is good; the NO_x reduction modelled is in agreement with the measured one, but data taken in the flame show that the flame structure is imperfectly represented.     

A USM turbulence-chemistry model for simulating NOx formation in turbulent combustion

A unified second-order moment (USM) turbulence-chemistry model for simulating NO_x formation in turbulent combustion is proposed. All the correlations, including the correlation of the reaction-rate coefficient fluctuation with the concentration fluctuation, are closed by the transport equations in the same form. This model abandons the series expansion approximation of the exponential term or the approximation of using a product of two single-variable PDFs instead of a joint PDF. The proposed model is used to simulate methane-air jet diffusion combustion and NO_x formation. The combustion prediction results are compared with those using the EBU-Arrhenius model and other two versions of the second-order moment model. The NO_x prediction results are compared with those using the pure presumed PDF model. Validation of predictions using the experimental data given by the Sandia National Laboratory, USA indicates that the proposed model gives better results than other models, and it is much economical than other refined models.     

Interactions of CO, HCl, and SOx in pulverised coal flames

The effect of HCl and SO₂ on CO oxidation in pulverised coal flames was investigated experimentally and kinetically in an entrained flow combustion reactor. Two bituminous coals (German ‘Goettelborn’ and a Polish coal) were used as fuels with a feeding rate of 1 or 1.5 kg/h. HCl or SO₂ is introduced into the reactor premixed with the primary air. Experimental results indicate that HCl addition may inhibit CO oxidation in coal flames and increases CO emission. Reducing temperature in the reactor will enhance the inhibitory effect of HCl on CO oxidation. The measured CO profiles along the reactor height clearly show that the addition of HCl may inhibit CO oxidation. In the experimental range of SO₂ addition, the inhibiting effect of SO₂ on CO oxidation is less significant than HCl. A detailed kinetic mechanism is used to model the reactions, and the controlling reactions are analysed.     

Attempts to reduce NOx exhaust emissions by using reformulated biodiesel

Biodiesel is a renewable, domestically produced fuel that has been shown to reduce particulate, hydrocarbon, and carbon monoxide emissions from diesel engines. Under some conditions, however, biodiesel produced from certain feedstocks has been shown to cause an increase in nitrogen oxides (NO_x). This is of special concern in urban areas that are subject to strict environmental regulations. Although soy-based biodiesel may increase the emission of nitrogen oxides, it is the most easily accessible in North America. We investigated two routes to reformulate soy-based biodiesel in an effort to reduce nitrogen oxide emissions. In one of these, soy-oil methyl esters were modified by conversion of a proportion of the cis bonds in the fatty acid chains of its methyl esters to their trans isomers. In the other approach, polyol derivatives of soybean oil were transesterified to form soy methyl polyol fatty acid esters. The NO_x emissions of these modified biodiesels were then examined, using a Yanmar L100 single cylinder, four stroke, naturally aspirated, air cooled, direct injection diesel engine. Using either isomerized methyl oleate or isomerized soy biodiesel, at 20% blend level in petroleum diesel (‘B20’), nitrogen oxide emissions were elevated by between 1.5 and 3 percentage points relative to the combustion of a B20 blend of commercial biodiesel. Nitrogen oxide emissions were reduced in proportion to blend level during the combustion of polyol biodiesel, with a 20% blend in petrodiesel resulting in a reduction of about 4.5 percentage points relative to the emissions of a comparable blend of commercial soy biodiesel.     

Numerical investigation of NOx emissions from a tangentially-fired utility boiler under conventional and overfire air operation

A CFD investigation has been carried out about the performance of a 600 MW_e tangentially coal-fired boiler, focusing on the reduction of NO_x attainable by using overfire air. To this purpose, a comprehensive combination of NO_x chemistry models has been used, coupled with the numerical simulation of fluid and particle flow, solid fuel combustion and heat and mass transfer. Predicted values of gas temperature and species concentration have been adopted to validate the model against actual measurements from the full-scale boiler, under conventional and overfire air arrangements. A reasonable agreement has been attained in most cases. Additionally, modelling sensitivity has been evaluated against variations in some fuel-dependent parameters hard to measure or estimate (devolatilisation rates, nitrogen content in volatiles and char, reburning rates). As a result, an analysis tool is available to study the response of this kind of boilers to a variety of coal feedstock and combustion conditions, in a feasible and economic manner.     

Optimisation of NOx reduction in advanced coal reburning systems and the effect of coal type

The advanced reburning process for NO_x emission control was studied in a down-fired 20 kW combustor by evaluating the performance of 15 pulverised coals as reburning fuels. The proximate volatile matter contents of the coals selected ranged from around 4 to 40 wt% (as received) with elemental nitrogen contents from around 0.6 to 2.0 wt%. The effects of reburn fuel fraction, reburning zone residence time, ammonia agent injection delay time (relative to the reburn fuel and burnout air injection points) and the nitrogen stoichiometric ratio are reported in detail and the optimum configurations for advanced reburning, established as a function of operating condition and coal type. The experimental results show that advanced reburning can reduce NO_x emissions up to 85%. The maximum benefits of advanced reburning over conventional reburning were observed at the lower reburn fuel fractions (around 10%). The results demonstrate that under advanced reburning conditions equivalent or higher levels of NO_x reduction can be achieved while operating the reburn zone closer to stoichiometric conditions compared with conventional reburning operating at high reburn fuel fractions (20-25%). Thus the practical problems associated with fuel-rich staged operation can be reduced. The effect of coal properties on the advanced reburning performance was also investigated. As with conventional reburning, the fuel nitrogen content of the coal used was found to have little influence on the NO_x reduction efficiency except at the highest reburn fuel fractions. There was, however, a strong correlation between the effectiveness of advanced reburning and the volatile content of the reburning fuels, which not only depended on the reburn fuel fraction, but also the mode (rich or lean) of advanced reburning operation. These parameters are mapped out experimentally to enable the best operating mode to be selected for advanced reburning as a function of the reburning fuel fraction and volatile content.     

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.     

Experimental measurements of the NOx and CO concentrations operating in oscillatory and non-oscillatory burning conditions

The effects of combustion driven acoustic oscillations in carbon monoxide and nitrogen oxides emission rates of a combustor operated with liquefied petroleum gas (LPG) were investigated. Because the fuel does not contain nitrogen, tests were also conducted with ammonia injected in the fuel, in order to study the formation of fuel NO_x. The main conclusions were: (a) the pulsating combustion process is more efficient than the non-pulsating one and (b) the pulsating combustion process generates higher rates of NO_x, with and without ammonia injection, as shown by CO and NO concentrations as function of the O₂ concentration. An increase in the LPG flow rate, keeping constant the air to fuel ratio, increased the acoustic pressure amplitude and the frequency of oscillation. The injection of ammonia had no influence on either pressure amplitude or frequency.     

Evaluation of the use of coal volatiles as reburning fuel for NOx reduction

In this study, computational fluid dynamic (CFD) and kinetic models were used to investigate the relative performances of coal volatiles and natural gas reburning. This modeling approach considers fluid dynamic and non-isothermal effects, which were not considered in past laboratory flow reactor studies. The commercial CFD code FLUENT 6.1 was used to predict the residence times and temperatures for reburning tests in the down-fired combustor (DFC), a 0.5 MMBTU/h research combustor at The Pennsylvania State University. To predict NO_x concentrations within the combustor, this data was then applied to an advanced reburning kinetic model used in past studies. For equal firing rates and stoichiometric ratios, reburning using methane yielded lower concentrations of NO_x (and, therefore, better NO_x reduction performance) than reburning using coal volatiles. The coal volatiles give increased flame temperature over natural gas, which apparently offsets the increased reburn zone hydrocarbon radical yield of coal volatiles over natural gas.     

Numerical analysis of pulverized coal combustion characteristics using advanced low-NOx burner

A three-dimensional numerical simulation is applied to a pulverized coal combustion field in a test furnace equipped with an advanced low-NO_x burner called CI-α burner, and the detailed combustion characteristics are investigated. In addition, the validities of the existing NO_x formation and reduction models are examined. The results show that a recirculation flow is formed in the high-gas-temperature region near the CI-α burner outlet, and this lengthens the residence time of coal particles in this high-temperature region, promotes the evolution of volatile matter and the progress of char reaction, and produces an extremely low-O₂ region for effective NO reduction. It is also found that, by lessening the effect of NO reduction in Levy et al.'s model and taking the NO formation from char N into account, the accuracy of the NO prediction is improved. The efficiency factor of the conversion of char N to NO affects the total NO concentration downstream after the injection of staged combustion air.     

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.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part V. Pyrolysis of a sewage sludge

A sewage sludge sample from a wastewater treatment plant in China was pyrolysed in a fluidised-bed/fixed-bed reactor and in a fluidised-bed/tubular reactor. HCN was found to be the main NO_x precursor, representing up to about 80% of the nitrogen present in the sludge. The thermal cracking of volatiles is the main route of HCN formation. NH₃ was also an important NO_x precursor formed during the pyrolysis of the sewage sludge. The experimental results indicate that there are at least two distinctive stages of NH₃ formation during the pyrolysis of the sewage sludge at a fast heating rate. The formation of NH₃ at temperatures lower than 400-500 °C is at least partly due to the amino structures in the sludge. The reactions of volatiles in the gas phase make negligible contributions to the observed NH₃ yield.