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.     

NO and N2O emissions from savanna soils following the first simulated rains of the season

Data on the emissions of oxides of nitrogen from the soil during the early part of the wet season are reported for nutrient-rich and nutrient-poor sandy soils at Nylsvley, South Africa. The emissions of NO_x and N₂O following the first wetting event of the season are elevated relative to subsequent events. The observed high emission rates (76 ng N-NO m^-2 s^-1) are partially attributed to the sandiness of the soil, which permits NO to diffuse out of the soil rapidly. The pulse of high emissions following wetting is maintained for approximately 72 hours, thereafter continuing at around 20 ng NO m^-2 s^-1 while the soil remains moist. The initial pulse is suggested to be due to the accumulation of a substrate pool during the dry period, coupled with an inability of plants and microbes to use it effectively during the first few days after wetting. There were no significant differences in the peak or subsequent emission rates for either NO or N₂O between two sites of differing nitrogen mineralisation potentials. N₂O emissions averaged 8% of NO_x emissions. The enhanced emissions of NO_x which follow the first wetting after a prolonged dry period do not make a very large contribution to the annual gaseous N emission budget, but could be a significant contributor to the high tropospheric ozone levels observed over southern Africa in springtime.     

N2O and NO emissions from grassland soils after the application of cattle and swine excreta

N₂O and NO fluxes from grassland soil after the application of cattle and swine excreta were measured by a closed chamber method in the autumn and winter of 1994 to 1995. Fresh excrement and urine were spread on the grassland experimental plots and these gas fluxes were measured one or two times a week. In the autumn experiment, N₂O and NO fluxes began to increase several days after the application, the NO flux reaching a maximum after 16 days. In the winter experiment, N₂O and NO fluxes began to increase 45 days after the application and reached a maximum after 80 days. Nitrous oxide flux was influenced by soil water content, high water content leading to high N₂O flux. The ratio of NO-N/N₂O-N in the flux was in the range of 1.1 to 13.7, and negatively correlated to the soil water content. In the winter experiment, the total emission rate of NO was 0.48% and 0.45% of total nitrogen in the applied cattle and swine excreta, respectively. The total emission rate of N₂O was 0.085% and 0.098% in the applied cattle and swine excreta, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synergetic NO reduction by biomass pyrolysis products simulating their reburning in circulating fluidized bed decoupling combustion

The present work investigated the synergetic effect of pyrolysis-derived char, tar and gas (py-gas) on NO reduction, which may occur in circulating fluidized-bed decoupling combustion (CFBDC) system treating N-rich fuel. Experiments were carried out in a lab-scale drop-tube reactor for NO reduction by some binary mixtures of reagents including char/py-gas, tar/py-gas and tar/char. At a specified total mass rate of 0.15 g·min^-1 for NO-reduction reagent, the char/py-gas (binary reagent) enabled the best synergetic NO reduction in comparison with the others. There existed effective interactions between char and some species in py-gas (i.e., H₂, C_xH_y) during NO reduction by pyrolysis products, meanwhile the tar/py-gas or tar/char mixture only caused a positive effect when tar proportion was necessarily lowered to about 26%. On the other hand, the synergetic effects were not improved for all tested binary reagents by increasing the reaction temperature and residence time.     

Carbonation of fly ash in oxy-fuel CFB combustion

Oxy-fuel combustion of fossil fuel is one of the most promising methods to produce a stream of concentrated CO₂ ready for sequestration. Oxy-fuel FBC (fluidized bed combustion) can use limestone as a sorbent for in situ capture of sulphur dioxide. Limestone will not calcine to CaO under typical oxy-fuel circulating FBC (CFBC) operating temperatures because of the high CO₂ partial pressures. However, for some fuels, such as anthracites and petroleum cokes, the typical combustion temperature is above 900 °C. At CO₂ concentrations of 80-85% (typical of oxy-fuel CFBC conditions with flue gas recycle) limestone still calcines, but when the ash cools to the calcination temperature, carbonation of fly ash deposited on cool surfaces may occur. This phenomenon has the potential to cause fouling of the heat transfer surfaces in the back end of the boiler, and to create serious operational difficulties. In this study, fly ash generated in a utility CFBC boiler was carbonated in a thermogravimetric analyzer (TGA) under conditions expected in an oxy-fuel CFBC. The temperature range investigated was from 250 to 800 °C with CO₂ concentration set at 80% and H₂O concentrations at 0%, 8% and 15%, and the rate and the extent of the carbonation reaction were determined. Both temperature and H₂O concentrations played important roles in determining the reaction rate and extent of carbonation. The results also showed that, in different temperature ranges, the carbonation of fly ash displayed different characteristics: in the range 400 °C < T ? 800 °C, the higher the temperature the higher the CaO-to-carbonate conversion ratio. The presence of H₂O in the gas phase always resulted in higher CaO conversion ratio than that obtainable without H₂O. For T ? 400 °C, no fly ash carbonation occurred without the presence of H₂O in the gas phase. However, on water vapour addition, carbonation was observed, even at 250 °C. For T ? 300 °C, small amounts of Ca(OH)₂ were found in the final product alongside CaCO₃. Here, the carbonation mechanism is discussed and the apparent activation energy for the overall reaction determined.     

NO emission on pulverized coal combustion in high temperature air from circulating fluidized bed – An experimental study

High temperature air was adopted by combustion in high excess air ratio in a circulating fluidized bed. Experiments on pulverized coal combustion in high temperature air from the circulating fluidized bed were carried out in a down-fired combustor with the diameter of 220 mm and the height of 3000 mm. The NO emission decreases with increasing the residence time of pulverized coal in the reducing zone, and the NO emission increases with excess air ratio, furnace temperature, coal mean size and oxygen concentration in high temperature air. The results also revealed that the co-existing of air-staging combustion with high temperature air is very effective to reduce nitrogen oxide emission for pulverized coal combustion in the down-fired combustor.     

Modeling NH3 and HCN emissions from biomass circulating fluidized bed gasifiers

A circulating fluidized bed biomass gasification model is developed in the present study. The model consists of sub-models for devolatilization, tar cracking and a chemical reaction network of main gasification reactions and nitrogen chemistry. A total of forty global chemical reactions are included in the model, of which twenty-eight reactions belong to fuel-nitrogen reaction network. Individual reaction rates are selected from the literature, wherever possible, based on studies of woody biomass fuels. Volatile nitrogen is assumed to consist of NH₃, HCN and N₂ with the distribution between three species as input parameters to the model. Modeling of the hydrodynamics of the riser is simplified by using solids concentration profile along the riser as an input to the model. Both gaseous phase and solids phase are assumed to be in plug flow. Modeling results are compared with the experimental results published in the literature. Predicted effects of bed temperature, equivalence ratio and fuel moisture content on main gaseous composition, tar and NH₃ emissions generally agree with the literature data. A sensitivity analysis of some reaction rates included in the model on NH₃ emissions has also been carried out. It has been revealed that the catalytic activity of bed materials towards the oxidation of NH₃ has the greatest influence on the predicted NH₃ emissions. In addition, the predicted NH₃ emissions are also affected by the catalytic activity of bed materials towards the decomposition of NH₃ and the homogenous reaction rates of NH₃ decomposition and the reduction of NO by NH₃ in the presence of oxygen.     

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.     

Particle flow, mixing, and chemical reaction in circulating fluidized bed absorbers

A mixing model has been developed to simulate the particle residence time distribution (RTD) in a circulating fluidized bed absorber (CFBA). Also, a gas/solid reaction model for sulfur dioxide (SO₂) removal by lime has been developed. For the reaction model that considers RTD distribution inside the core and annulus regions of a CFBA, a macrochemical reaction can be simulated based on microchemical reaction dynamics. The presented model can predict SO₂ and lime concentration distributions inside the CFBA, and give the amount of lime needed to remove a given percentage of SO₂. It is found that SO₂ concentration decreases with the increase of CFBA distance from the bottom in the core region. However, lime concentration exhibits a very slight variation in the core region. This means that lime is efficiently utilized to remove SO₂. The model also predicts that SO₂ partial pressure at the exit of the CFBA decreases with the increase in the percentage of fresh lime injected in the CFBA.     

Flue gas desulfurization in an internally circulating fluidized bed reactor

An internally circulating fluidized bed reactor (ICFBR) was used as a desulfurization apparatus in this study. The height of the bed was 2.5 m, and the inner diameter was 9 cm. The bed materials were calcium sorbent and silica sand. The effects of the operating parameters of the flue gas desulfurization including relative humidity, particle size of the calcium sorbent, inlet concentration of SO₂, difference between the superficial gas velocities in the draft tube and the annulus, and superficial gas velocity in the draft tube on SO₂ removal efficiency (RE) were investigated. It was found that when the relative humidity (RH) was varied from 40% to 80%, the steady state RE had a largest value of approximately 15% when the relative humidity was 60%. When RH = 50%, 60% and 70%, RE decreased initially and then increased. After that RE decreased again until a steady state was reached. In addition, RE decreased with increasing calcium particle size or inlet SO₂ concentration. A larger difference between the superficial gas velocities in the draft tube and the annulus had a higher RE resulting from increasing reactivity of the calcium sorbent caused by a higher attrition rate. Moreover, a higher attrition rate had a higher total volume of the flue gas treated. Finally, a model to predict the steady state RE in ICFBR was proposed. It assumed that the draft tube section was a bubbling fluidized bed while the annulus section was a moving bed. In addition, the effects of the calcium sorbent conversion, attrition rate and gas-bypassing fractions on RE were also taken into account in this model. It was found that the values of RE predicted by this model agreed with the experimental results.     

The NO and N2O formation mechanism under circulating fluidized bed combustor conditions: From the single particle to the pilot-scale

The NO and N₂O formation mechanism is studied starting from a single fuel particle burning under well-defined conditions up to a pilot-scale circulating fluidized bed combustor (CFBC). The fuel, petroleum coke, was the same in all tests and care has been taken to obtain chemical similarity between the different units: a formation rate unit, a laboratory-scale and a pilot-scale CFBC. A detailed single particle NO/N₂O formation model has been developed and incorporated in a CFBC NO/N₂O emission model. To thoroughly test the modeled NO/N₂O mechanism, the iodine addition method has been used in all units.     

Experimental validation of packed bed chemical-looping combustion

Chemical-looping combustion has emerged as a promising alternative technology, intrinsically integrating CO₂ capture in power production. A novel reactor concept based on dynamically operated packed beds has been proposed [Noorman, S., van Sint Annaland, M., Kuipers, J.A.M., 2007. Packed bed reactor technology for chemical-looping combustion. Ind. Eng. Chem. Res. 46, 4212-4220] and in this work, packed bed chemical-looping combustion was investigated experimentally to provide an experimental proof-of-principle. Using information obtained from both the reduction and oxidation cycles, the measured maximum temperature rise and front velocities in the packed bed during the oxidation cycle corresponded very well with analytical expressions describing the system, especially when the contribution of the formation of carbon during the reduction cycle was taken into account.     

Gas leakage measurements in a cold model of an interconnected fluidized bed for chemical-looping combustion

In chemical-looping combustion (CLC) a gaseous fuel is burnt with inherent separation of the greenhouse gas carbon dioxide. The oxygen is transported from the combustion air to the fuel by means of metal oxide particles acting as oxygen carriers. A CLC system can be designed similar to a circulating fluidized bed, but with the addition of a bubbling fluidized bed on the return side. Thus, the system consists of a riser (fast fluidized bed) acting as the air reactor. This is connected to a cyclone, where the particles and the gas from the air reactor are separated. The particles fall down into a second fluidized bed, the fuel reactor, and are via a fluidized pot-seal transported back into the riser. The gas leaving the air reactor consists of nitrogen and unreacted oxygen, while the reaction products, carbon dioxide and water, come out from the fuel reactor. The water can easily be condensed and removed, and the remaining carbon dioxide can be liquefied for subsequent sequestration.The gas leakage between the reactors must be minimized to prevent the carbon dioxide from being diluted with nitrogen, or to prevent carbon dioxide from leaking to the air reactor decreasing the efficiency of carbon dioxide capture. In this system, the possible gas leakages are: (i) from the fuel reactor to the cyclone and to the pot-seal, (ii) from the cyclone down to the fuel reactor, (iii) from the pot-seal to the fuel reactor. These gas leakages were investigated in a scaled cold model. A typical leakage from the fuel reactor was 2%, i.e. a CO₂ capture efficiency of 98%. No leakage was detected from the cyclone to the fuel reactor. Thus, all product gas from the air reactor leaves the system from the cyclone. A typical leakage from the pot-seal into the fuel reactor was 6%, which corresponds to 0.3% of the total air added to the system, and would give a dilution of the CO₂ produced by approximately 6% air. However, this gas leakage can be avoided by using steam, instead of air, to fluidize the whole, or part of, the pot-seal. The disadvantages of diluting the CO₂ are likely to motivate the use of steam.     

Removal of NO and SO2 by pulsed corona discharge process

Overall examination was made on the removal of NO and SO₂, by pulsed corona discharge process. The mechanism for the removal of NO was found to largely depend on the gas composition. In the absence of oxygen, most of the NO removed was reduced to N₂; on the other hand, oxidation of NO to NO₂ was dominant in the presence of oxygen even when the content was low. Water vapor was an important ingredient for the oxidation of NO₂, to nitric acid rather than that of NO to NO₂. The removal of NO only slightly increased with the concentration of ammonia while the effect of ammonia on the removal of SO₂ was very significant. The energy density (power delivered/feed gas flow rate) can be a measure for the degree of removal of NO. Regardless of the applied voltage and the flow rate of the feed gas stream, the amount of NO removed was identical at the same energy density. The production of N₂O increased with the pulse repetition rate, and the presence of NH₃ and SO₂ enhanced it. Byproducts generated from propene used as additive were identified and analyzed. The main byproducts other than carbon oxides were found to be ethane and formaldehyde, but their concentrations were negligibly small.     

An overview: Comparative kinetic behaviour of Pt, Rh and Pd in the NO + CO and NO + H2 reactions

This paper reports a comparative kinetic investigation of the overall reduction of NO in the presence of CO or H₂ over supported Pt-, Rh- and Pd-based catalysts. Different activity sequences have been established for the NO+H₂ reaction Pt/Al₂O₃>Pd/Al₂O₃>Rh/Al₂O₃ and for the NO+CO reaction Rh/Al₂O₃>Pd/Al₂O₃> Pt/Al₂O₃. It was found that both reactions differ from the rate determining step usually ascribed to the dissociation of chemisorbed NO molecules. The rate enhancement observed for the NO+H₂ reaction has been mainly related to the involvement of a dissociation step of chemisorbed NO molecules assisted by adjacent chemisorbed H atoms. The calculation of the kinetic and thermodynamic constants from steady-state rate measurements and subsequent comparisons show that Pd and Rh are predominantly covered by chemisorbed NO molecules in our operating conditions which could explain either changes in activity or in selectivity with the lack of ammonia formation on Rh/Al₂O₃ during the NO+H₂ reaction. Interestingly, Pd and Rh exhibit similar selectivity behaviour towards the production of nitrous oxide (N₂O) irrespective of the nature of the reducing agent (CO or H₂). A weak partial pressure dependency of the selectivity is observed which can be related to the predominant formation of N₂ via a reaction between chemisorbed NO molecules and N atoms, while over Pt-based catalysts the associative desorption of two adjacent N atoms would occur simultaneously. Such tendencies are still observed under lean conditions in the presence of an excess of oxygen. However, a detrimental effect is observed on the selectivity with an enhancement of the competitive H₂+O₂ reaction, and on the activity behaviour with a strong oxygen inhibiting effect on the rate of NO conversion, particularly on Rh.     

Chemical kinetic modelling of the effect of NO on the oxidation of CH4 under fluidized bed combustor conditions

The ignition and burnout of the volatiles in fluidized bed combustor are essential for its performance and emissions. NO_x are known to sensitize the oxidation of hydrocarbons, CO, and H₂. This effect is relevant especially for fluidized bed combustors, which are operated at relatively low temperatures (i.e. about 850 °C). Different reaction mechanisms and modifications to existing mechanisms have been proposed in the literature to account for these low temperature interactions of NO_x and hydrocarbons. In this work, an existing widely used reaction mechanism is adapted and tested for its capability to describe the NO sensitized oxidation of CH₄ under conditions relevant to fluidized bed combustion. NO lowers the ignition temperature to about 300 °C under the conditions investigated. Three different oxidation paths for the oxidation of CH₄ have been identified and discussed. Their relative importance strongly depends on combustion temperature, indicating that the presence of NO_x significantly affects the oxidation of the volatiles in fluidized bed combustion.     

Olive cake combustion in a circulating fluidized bed

In this study, a circulating fluidized bed of 125 mm diameter and 1800 mm height was used to find the combustion characteristics of olive cake (OC) produced in Turkey. A lignite coal that is most widely used in Turkey was also burned in the same combustor. The combustion experiments were carried out with various excess air ratios. The excess air ratio, λ, has been changed between 1.1 and 2.16. Temperature distribution along the bed was measured with thermocouples. On-line concentrations of O₂, SO₂, CO₂, CO, NO_x and total hydrocarbons were measured in the flue gas. Combustion efficiencies of OC and lignite coal are calculated, and the optimum conditions for operating parameters are discussed. The combustion efficiency of OC changes between 82.25 and 98.66% depending on the excess air ratio. There is a sharp decrease observed in the combustion losses due to hydrocarbons and CO as the excess air ratio increases. The minimum emissions are observed at λ=1.35. Combustion losses due to unburned carbon in the bed material do not exceed 1.4 wt% for OC and 1.85 wt% for coal. The combustion efficiency for coal changes between 82.25 and 98.66% for various excess air ratios used in the study. The ash analysis for OC is carried out to find the suitability of OC ash to be used as fertilizer. The ash does not contain any hazardous metal.     

Photocatalytic oxidation of ethyl alcohol in an annulus fluidized bed reactor

The photocatalytic oxidation of ethyl alcohol vapor in an annulus fluidized bed reactor of 0.06 m I.D. and 1.0 m long was examined. The TiO₂ catalyst employed was prepared by the sol-gel method and was coated on the silica gel powder. The UV lamp was installed at the center of the bed as the light source. The effects of the initial concentration of ethyl alcohol, the power of UV-lamp, the photocatalysts with different preparation methods, and the superficial gas velocity on the reaction rate of ethyl alcohol decomposition were determined. It was found that, at 1.2 U_mf of flow rate, about 80% of ethyl alcohol was decomposed with initial concentration of 10,000 ppmv and the increase of superficial gas velocity reduced the reaction rate significantly.     

Co-gasification of coal and wood in a dual fluidized bed gasifier

In the last decade the reduction of CO₂ emissions from fossil fuels became a worldwide topic. Co-gasification of coal and wood provides an opportunity to combine the advantages of the well-researched usage of fossil fuels such as coal with CO₂-neutral biomass. Gasification itself is a technology with many advantages. The producer gas can be used in many ways; for electric power generation in a gas engine or gas turbine, for Fischer-Tropsch synthesis of liquid fuels and also for production of gaseous products such as synthetic natural gas (bio SNG). Moreover, the use of the producer gas in fuel cells is under investigation. The mixture of coal and wood leads to the opportunity to choose the gas composition as best befits the desired process. Within this study the focus of investigation was of gasification of coal and wood in various ratios and the resulting changes in producer gas composition. Co-gasification of coal and wood leads to linear producer gas composition changes with linear changing load ratios (coal/wood). Hydrogen concentrations rise with increasing coal ratio, while CO concentrations decrease. Due to the lower sulfur and nitrogen content of wood, levels of the impurities NH₃ and H₂S in the producer gas fall with decreasing coal ratio. It is also shown that the majority of sulfur is released in the gasification zone and, therefore, no further cleaning of the flue gas is necessary. All mixture ratios, from 100 energy% to 0 energy% coal, performed well in the 100 kW dual fluidized bed gasifier. Although the gasifier was originally designed for wood, an addition of coal as fuel in industrial sized plants based on the same technology should pose no problems.     

Modelling of circulating fluidized bed combustion of a char

The combustion of a char in the 41 mm ID riser of a laboratory circulating fluidized bed combustor has been investigated at different air excesses and rates of solids (char and sand) circulating in the loop. Riser performance was characterized by an axial oxygen concentration profile as well as by the overall carbon content and particle size distribution. The proposed model accounts for carbon surface reaction, intraparticle and external diffusion, and attrition. External diffusion effects were relevant in the riser dense region where char was potentially entrapped in large clusters of inert solids. Experimental data and results of the model calculations are in satisfactory agreement.