Efficient and cost effective reburning using common wastes as fuel and additives

Potential substitutes of natural gas and lignite fly ash as NO and HCN reducing agents, respectively, for heterogeneous reburning were examined in a bench-scale apparatus equipped with a simulated reburning and a burnout furnace. Selection of NO reducing agent is based on fuel volatility and nitrogen functionality. HCN reducing agent selection is based on literature data. A wide range of waste materials and industrial by-products show overall NO reduction efficiency up to 88% at reburning stoichiometric ratio 0.90 or 0.95. Mixed fuel containing scrap tire and Fe₂O₃ is particularly effective. Though its cost is constrained by the energy-intensive operation of grinding the tire, the estimated raw-material cost is better than that of natural gas reburning and highly competitive against SCR. A first-level approximation study of the selectivities of nitrogen species to form NO in burnout zone reveals the importance of HCN and char nitrogen reaction mechanisms.     

Detailed measurements in a laboratory furnace with reburning

This article presents a detailed experimental characterization of the reburning process in a large-scale laboratory furnace. Natural gas, pine sawdust and pulverized coal were used as reburn fuels. Initially, the study involved the collection of in-flame combustion data, without reburning, in order to define appropriate locations for the injection of the reburn fuels. Next, flue-gas data were obtained for a wide range of experimental conditions using the three reburn fuels and, subsequently, detailed measurements of local mean O₂, CO, CO₂, HC and NO_x concentrations, and gas temperatures have been obtained in the reburn zone for three representative furnace operating conditions, one for each reburn fuel studied. The flue-gas data revealed that the sawdust reburning leads to NO_x reductions comparable or even higher than those attained with natural gas reburning, while coal reburning yields much lower NO_x reductions. The detailed data obtained in the reburn zone indicates that the reburning process remains active throughout all the reburn zone in the cases of natural gas and sawdust reburning, while in the case of coal reburning its relatively low volatile matter content is insufficient to establish an effective reburn zone. In the cases of the sawdust and coal reburning the burnout levels remain approximately constant, regardless of the NO_x emissions reduction, with the sawdust reburning leading to higher particle burnout performance than the coal reburning.     

Kinetic model for natural gas reburning

Kinetics of natural gas reburning is modeled on the basis of GRI3.0 and the method of Gear. The calculation results indicate that the model agrees with experiments. HCN, NH_i and HCCO play an important role in the reburning system. Injecting NH₃ and increasing the fraction of HCCO in the reburning system will promote NO reduction. Injecting natural gas at the places wherein the fraction of NO is highest is a benefit to de-NOx. There exists an optimal value of ratio of natural gas: NO for reburning system. The influences of temperature, excess oxygen ratio and pressure are also discussed in the reburning system.     

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.     

Application of gaseous fuel reburning for controlling nitric oxide emissions in boilers

An experimental study was performed on a 36 kW_th down-fired furnace in order to obtain a wider and more detailed knowledge of the influence of the key parameters on the gaseous fuel reburning process when typical Chinese coals served as the primary fuel. The experimental results show that both above 50% nitric oxide reduction and low carbon loss can be obtained when reburn zone residence time is about 0.6 s–0.9 s, gaseous reburn fuel percent is about 10%–15% and average excess air coefficient of reburn zone is about 0.8–0.9. According to the optimizational reburning operating parameters, a 350 MW_e coal-fired boiler was retrofitted for reburning application. The retrofitted boiler had about 0.7 s reburn zone residence time and about 2 s residence time after the burnout air was injected. The results of the demonstration on the full-scale boiler showed that the nitric oxide emission was about 235 mg/Nm³ (O₂ = 3%, dry) from the retrofitted boiler and above 60% nitric oxide reduction efficiency could be achieved with no adverse effects on the boiler operability when the coke-oven gas used as the reburn fuel. This successful demonstration project filled the gaps in the gaseous fuel reburning application on 300 MW_e grade unit boiler in China and showed that the values of the optimizational reburning parameters obtained from experiments could be successfully applied to the designing, retrofitting and optimizing for the gaseous fuel reburning process.     

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.     

An experimental parametric study of gas reburning under conditions of interest for oxy-fuel combustion

An experimental parametric study on the NO reduction efficiency by reburning under oxy-fuel conditions has been performed through the gas-phase interactions between different gas mixtures and NO in a CO₂ atmosphere, under flow reactor conditions in the 800-1800 K temperature range. The study provides a wide amount of experimental data on reburning under oxy-fuel conditions to be further used in modeling studies. A higher NO reduction is attained in a N₂ atmosphere compared to CO₂ under fuel-rich and stoichiometric conditions, although the efficiency is similar in both atmospheres under fuel-lean conditions. The formation of HCN in a fuel-rich environment is higher in N₂ than in CO₂ but comparable for other stoichiometries. The influence of the main parameters of the process under oxy-fuel conditions has been found to present similar trends to those observed in literature for reburning in air. A significant NO reduction can be obtained at moderately high temperatures, fuel-rich conditions, high values of the reburn fuel/NO ratio, sufficiently high residence times and low water vapor contents. C₂H₆ has been detected to act as a better reburn fuel as CH₄, whereas CO itself is unable to reduce NO.     

Effect of Mixing on Natural Gas Reburning

The purpose of this work is to understand the influence of the mixing process on reburning performance. Modeling is done in a one-dimensional approximation by utilizing a detailed chemical mechanism, staged addition of reactants, and mixture stratification. Natural gas is used as both the main fuel and the reburning fuel. The most important parameters that affect the efficiency of the reburning process are: the amount of the reburning fuel, the initial NO level, the initial temperatures of the injected reburning fuel and overfire air (OFA), temperature of flue gas at the points where reburning fuel and OFA are injected, and intensity of mixing of the reburning fuel and OFA with the stream of flue gases. It is shown that fuel stratification in the mixing zone improves reburning efficiency for small heat inputs of the reburning fuel and degrades reburning efficiency for large heat inputs. Initial temperatures of the reburning fuel and OFA affect NO reduction and can be optimized for deeper NO control. Reactions of N-containing species in the burnout zone play an important role in NO reduction for large heat inputs of the reburning fuel.     

水蒸气对煤粉再燃还原NO的影响

在兖州烟煤煤粉再燃还原NO的固定床反应器试验中加入不同量的水蒸汽,研究了水蒸汽对煤粉再燃还原NO的影响。结果表明,水蒸汽的加入加快了煤粉再燃还原NO的速度,但单位质量煤粉的还原效果随水蒸汽量的增加而降低,原因是水蒸汽同时也加速了煤粉的燃尽。水蒸汽加快了CO和CO2生成速度以及O2消耗速度,在挥发分为主的反应阶段促进CO2的生成更明显,而在焦炭为主的反应阶段促进CO的生成更明显,但单位质量煤粉的CO2生成量和O2消耗量均降低、CO生成量增加。煤粉再燃的燃尽时间随水蒸汽量的增加而缩短,比如当水蒸汽量为2%时,燃尽时间缩短了25.9%,当水蒸汽量为4%时,燃尽时间缩短了47.8%。在再燃区加入一定量的水蒸汽,既能改善煤粉对NO的还原效果,又能提高煤粉的燃尽率。工程应用要根据煤质特点、主燃区NO浓度、再燃煤粉比例、再燃区过量空气系数、经济性评价等因素进行试验确定最佳水蒸汽量。     

Experimental and kinetic modeling study of the reduction of NO by hydrocarbons and interactions with SO2 in a JSR at 1 atm

The reduction of nitric oxide (NO) by a mixture of methane, ethylene and acetylene with and without addition of SO₂ has been studied in a fused silica jet-stirred reactor operating at 1 atm in simulated conditions of the reburning zone. The temperatures were ranging from 800 to 1400 K. In these experiments, the initial mole fractions of NO and SO₂ were 0 or 1000 ppm, that of methane, ethylene and acetylene were, respectively, 2400, 1200 and 600 ppm. The equivalence ratio has been varied from 0.5 to 2.5. It was demonstrated that the reduction of NO varies as the temperature and that for a given temperature, a maximum NO reduction occurs slightly above stoichiometric conditions. The addition of SO₂ inhibited the process of reduction of NO under the present conditions. The present results generally follow those obtained in previous studies involving simple hydrocarbons or natural gas as reburn fuel. A detailed chemical kinetic modeling of the present experiments was performed using an updated and improved kinetic scheme (1006 reversible reactions and 145 species). An overall reasonable agreement between the present data and the modeling was obtained. Also, the proposed kinetic mechanism can be successfully used to model the reduction of NO by ethane, ethylene, a natural gas blend (methane-ethane 10:1). The kinetic modeling indicates that the reduction of NO proceeds via the following sequence of reactions: HCCO+NO=HCNO+CO; HCCO+NO=HCN+CO₂; HCN+O=NCO+H; HCN+O=NH+CO; HCN+H=CN+H₂; HCNO+H=HCN+OH; CN+O₂=NCO+O; NCO+H=NH+CO; NCO+NO=N₂O+CO; NCO+NO=CO₂+N₂; NH+NO=N₂O+H; NH+NO=N₂+OH. The inhibition of this process by SO₂ is explained by the sequence of reactions H+SO₂+M=HOSO+M and HOSO+H=SO₂+H₂ that acts as a termination process: H+H+M=H₂+M.     

The evaluation of waste tyre pulverised fuel for NOx reduction by reburning

The combustion of coal for power generation will continue to play a major role in the future, however, this must be achieved using cleaner technologies than we use at present. Scrap tyre arisings in the UK are 400,000 tonnes per year amounting to 30 million tyres and in the EU as a whole, more than 2.5 million tonnes of tyres per year are scrapped. The recent EC Waste Landfill Directive (1999) sets a deadline for the banning of whole and shredded tyres from landfill sites by 2006. Consequently, there is an urgent need to find a mass disposal route for tyres. We describe, in this paper, a novel use for tyre rubber pulverised fuel in a NO_x reburning process which may have an application in power station boilers. This method of disposal could represent a way of combining waste disposal, energy recovery and pollution control within one process. A preliminary study of micronised tyre combustion was undertaken to identify the suitable size ranges for application in NO_x reduction by reburning. Tests were performed in a down-fired, pulverised fuel combustor (PFC) operating at about 80 kW. Superior combustion characteristics, i.e. burnout were achieved with particle sizes less than 250 μm. A South African coal was used as the primary fuel in the reburn tests and the tyre was fed pneumatically via a separate feed system. Parameters studied, were, reburn zone stoichiometry and reburn fuel fraction. Additionally, the carbon content of the ash was carefully monitored for any effect on burnout at the fuel rich reburn stoichiometries. The NO_x reductions achieved with tyres are compared with reburning with coal. NO_x reductions up to 80% were achieved with tyres at half of the reburn fuel feed rate required to achieve the same reductions by coal. The results have been evaluated within the context of other studies available in the literature on NO_x reburning by bituminous coal, brown coal, gas and biomass.     

Evaluation of the use of different hydrocarbon fuels for gas reburning

Gas reburning is a NO_x reduction technique that has been demonstrated to be efficient in different combustion systems. An experimental study of gas reburning performance in the low temperature range (at and under 1100°C) has been carried out. An evaluation of the use of different hydrocarbon fuels, such as natural gas, methane, ethane, ethylene and acetylene was performed and the influence of the temperature and stoichiometry is considered. The results show that the reburning process is effective under appropriate conditions at the low temperatures used in this work. However, as the temperature diminishes, the influence of the reburn fuel becomes more marked and the use of acetylene or ethane and ethylene leads to better performance than natural gas or methane, the classical reburn fuels for high temperature applications.     

The effect of the calcium in lignite on its effectiveness as a reburn fuel

The effect of the calcium present in lignite on the effectiveness of NO reduction in the reburning method has been studied in the 900-1100 °C temperature range. Lignites from three Polish mines were used. The experiments were carried out in a laboratory scale drop-tube furnace reactor. The demineralised lignites were loaded with Ca using: calcium acetate Ca(CH₃COO)₂, calcium hydroxide Ca(OH)₂ and calcium carbonate CaCO₃. For the reburning process the catalytic effect of the presence of calcium in lignite was found to be rather modest (approx. ±20%) in the temperature range studied. It was shown that up to 1000 °C the calcium added to the demineralised lignites improved their effectiveness as reburn fuels. The effect was almost reversed when the reburn temperature was raised to 1100 °C. With the impregnated lignites the extent of NO reduction appeared to be practically independent of the calcium compound used. Mineral matter in raw lignite exerts a similar catalytic effect to calcium introduced by impregnation.     

Calcium-based sorbents for simultaneous NOx/SOx reduction in a down-fired furnace

The performance of a suite of different carboxylic salts of calcium, have been assessed as dual NO_x/SO_x reducing agents. The salts studied include, calcium magnesium acetate (CMA), calcium acetate (CA), calcium formate (CF), calcium benzoate (CB), calcium propionate (CP) and magnesium acetate (MA). The primary fuel was propane operating with a primary zone stoichiometry fixed at λ₁=1.05 and the reburn zone stoichiometry, λ₂, was varied between 1.03 and 0.86. Overall stoichiometry, λ₃, was 1.15. CMA was also tested using a US Blend coal as the primary fuel. Experiments were performed in a down-fired pulverised coal furnace operating at an output of 80 kWth. Results showed that CMA and CP were the best dual NO_x/SO₂ performers followed by CB, CA, MA and CF. Also, the co-injection of urea with the carboxylic salts as an advanced reburning agent was studied. The results showed that real improvements in NO reduction over basic reburning of greater than 70% could be obtained depending to a large extent on the initial effectiveness of the reburn fuel as well as nitrogen stoichiometric ratio within the reburn zone. Decomposition of the carboxylic salts was studied by thermo-gravimetric analysis (TGA) yielding information on the release of organic fractions important as precursors for CH_i radical formation. Examination of structural and thermo-chemical properties of the carboxylic salts identified a correlation of NO reduction under reburning conditions with volatile organic content. Calcium magnesium acetate and calcium propionate showed superior SO₂ capture ability with reductions greater than 70% at Ca/S above 2, around 20% higher than calcium acetate and calcium formate. Magnesium acetate achieved reductions of less than 10% at Mg/S ratios up to 2.5. There is a clear difference in the potential effectiveness of the sorbents as dual NO_x/SO₂ reductants, since the organic input for a given Ca input varies according to the composition of the sorbent. Some compromise may have to be made when choosing the correct operating conditions since good reductions in SO₂ may not give acceptable NO_x reductions. However, the application of advanced reburning under these conditions has been shown here to compensate for low initial NO_x reductions by basic reburning.     

Impacts of acid gases on mercury oxidation across SCR catalyst

A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO₂, and SO₃ on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O₂, CO₂, H₂O, NO, NO₂, and NH₃, and N₂. HCl, SO₂, and SO₃ were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5–50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO₂ and SO₃ showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO₂ and SO₃, by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO₂ (2000 ppm), and SO₃ (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst.     

Detailed measurements in a pulverized-coal-fired large-scale laboratory furnace with air staging

The aim of the present work was to evaluate the performance of a pulverized-coal-fired large-scale laboratory furnace with air staging. New data are reported for gas phase species concentration, temperature and particle burnout for two primary zone stoichiometric ratios, 1.15 (unstaged flame) and 0.95 (staged flame), other operating conditions being fixed. The results revealed that the reduction in primary zone stoichiometric ratio caused a decrease in NO_x emissions from 421 to 180 mg/N m³@6%O₂, an increase in CO emissions from 51 to 168 mg/N m³@6%O₂ and a reduction in particle burnout from 81.8% to 76.5%. It was concluded that the reduction of the O₂ availability in the primary zone inhibits the NO formation, mainly via the fuel mechanism, but it affects negatively both the CO and the char oxidation processes because, under staging conditions, both processes tend to occur in the vicinity of the over fire air injection region, where the temperatures are relatively low.     

Optimization of coal reburning in a 1 MW tangentially fired furnace

This paper deals with an experimental study on the influence of coal reburn on NO_x reduction efficiency, unburned carbon in fly ash and the furnace temperature distribution along the height in a 1 MW (heat input power) tangentially firing furnace with multiple low NO_x control technologies. Several variables associated with the reburn system have been investigated in the experiment which includes the air stoichiometry in reburn zone, the location of reburn burner and reburn coal fineness. The optimum location of reburn nozzles has been found where NO_x reduction efficiency is highest. With the decrease of reburn coal size (average diameter from 53.69 μm to 11.47 μm), NO_x reduction efficiency increases slightly, but the burnout performance of coal is improved noticeably. In the process of coal reburning, the temperature of flue gas is 70–90 °C lower in primary combustion, but 130–150 °C higher at the top of furnace as compared to baseline.     

Reduction of NO in the exhaust gas by reaction with N radicals

N atoms can serve as a reducing agent for NO in the exhaust gases from fossil fuel power plants. In order to investigate the reduction of NO, synthetic exhaust gas was plasma treated in a dielectric barrier discharge (DBD) (direct treatment) as well as treated by adding nitrogen atoms generated in a pure nitrogen DBD (remote treatment). A DBD with a coaxial electrode geometry was used. Oxygen could be added to the synthetic exhaust. A complete NO reduction was achieved in dry, oxygen free exhaust gas with direct treatment, but oxygen and humidity in the exhaust gas promotes formation of N_xO_y and reduces the efficiency of NO reduction. A 90% NO reduction was achieved with remote treatment. Remote treatment is insensitive to oxygen in the exhaust, but requires large amounts of nitrogen and energy. Fourier transform infrared spectroscopy and ultraviolet absorption spectroscopy were employed in order to detect NO, NO₂, and N₂O in the treated exhaust gas stream.     

Reduction of NO by activated carbon in the presence of vanadium

The NO reduction characteristics of a vanadium supported activated carbon catalyst have been examined without addition of reducing agent (i.e., ammonia, NH₃). The catalyst was prepared from commercial coconut activated carbon that was impregnated with 2.8 wt.% vanadium. The NO reduction reactions were conducted under conditions with 3% O₂ and without O₂ in a fixed bed reactor. In the condition with O₂, 84% NO conversion resulted at 360 °C, though the catalyst began to burnout at a temperature higher than 300 °C and with large quantities of CO and CO₂ being emitted. In the condition without O₂, the burnout of the catalyst was insignificant and resulted in small amounts of CO and CO₂. The NO conversion increased gradually with the reaction temperature reaching 78% at 450 °C. SEM photographs and BET measurements are useful tools for understanding the burnout phenomena with the catalyst. The burnout in the condition with O₂ resulted in the catalyst rapidly losing its activity. However, in the condition without O₂, the catalyst gradually lost its activity and finally approached a steady state. Moreover, the modified mechanism scheme of the NO reduction reactions without NH₃ and with the catalyst is described and the global rate equation for the reaction without O₂ is obtained.     

The effect of nitrogen oxides in air on the performance of proton exchange membrane fuel cell

The effects of NO_x on the performance of proton exchange membrane (PEM) fuel cell were investigated through the introduction of a mixture containing NO and NO₂, in a ratio of 9:1, into the cathode stream of a single PEM fuel cell. The NO_x concentrations used in the experiments were 1480 ppm, 140 ppm and 10 ppm, which cover a range of three orders. The experimental results obtained from the tests of durability, polarization, reversibility and electrochemical impedance spectroscopy (EIS) showed a detrimental effect of NO_x on the cell performance. The electrochemical measurements results suggested that the impacts of NO_x are mainly resulted from the superposition of the oxygen reduction reaction (ORR), NO and HNO₂ oxidation reactions, and the increased cathodic impedance. Complete recovery of the cell performance was reached after operating the cell with clean air and then purging with N₂ for hours.