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.     

Conversions of fuel-N,volatile-N,and char-N to NO and N2O during combustion of a single coal particle in O2/N2 and O2/H2O at low temperature

Oxy-steam combustion is a promising next-generation combustion technology. Conversions of fuel-N, volatile-N, and char-N to NO and N₂O during combustion of a single coal particle in O₂/N₂ and O₂/H₂O were studied in a tube reactor at low temperature. In O₂/N₂, NO reaches the maximum value in the devolatilization stage and N₂O reaches the maximum value in the char combustion stage. In O₂/H₂O, both NO and N₂O reach the maximum values in the char combustion stage. The total conversion ratios of fuel-N to NO and N₂O in O₂/N₂ are obviously higher than those in O₂/H₂O, due to the reduction of H₂O on NO and N₂O. Temperature changes the trade-off between NO and N₂O. In O₂/N₂ and O₂/H₂O, the conversion ratios of fuel-N, volatile-N, and char-N to NO increase with increasing temperature, and those to N₂O show the opposite trends. The conversion ratios of fuel-N, volatile-N, and char-N to NO reach the maximum values at < O₂ > = 30 vol% in O₂/N₂. In O₂/H₂O, the conversion ratios of fuel-N and char-N to NO reach the maximum values at < O₂ > = 30 vol%, and the conversion ratio of volatile-N to NO shows a slightly increasing trend with increasing oxygen concentration. The conversion ratios of fuel-N, volatile-N, and char-N to N₂O decrease with increasing oxygen concentration in both atmospheres. A higher coal rank has higher conversion ratios of fuel-N to NO and N₂O. Anthracite coal exhibits the highest conversion ratios of fuel-N, volatile-N, and char-N to NO and N₂O in both atmospheres. This work is to develop efficient ways to understand and control NO and N₂O emissions for a clean and sustainable atmosphere.     

Effect of Na,Ca and Fe on the evolution of nitrogen species during pyrolysis and combustion of model chars

The catalytic effects of Na, Ca and Fe on the formation of HCN and NH₃ during pyrolysis of nitrogen-containing model chars and on the emission of NO_x during the char combustion have been investigated in a fixed bed reactor. The results show that fuel-type nitrogen is mainly retained in char under the pyrolysis conditions (∼900 °C). The presence of Na favors the transformation of char-nitrogen to volatile-nitrogen at high temperature, but the influence of Ca and Fe is negligible. The NH₃:HCN ratio under catalytic pyrolysis conditions is higher than that under non-catalytic pyrolysis conditions. It was also found that the emission of NO_x was restrained under catalytic conditions at high combustion temperature, but was favored at low temperature. The conversion of char-N to NO_x depended on a number of factors including the properties of char, the types of catalysts and the combustion conditions. The influence of catalysts on the emission levels of NO_x reflects the relative importance of the catalytic effect on char-N oxidation and on NO-char reaction during the combustion of nitrogen-containing char.     

模拟分解炉中煤焦燃烧生成NO的特性

对国内水泥行业中几种煤焦在模拟的分解炉中NO生成特性进行了研究,考察了煤种、温度、生料对焦炭氮的释放特性的影响,探讨了焦炭氮在工业分解炉中的释放机理.研究结果表明,不同煤种的NO生成特性有较大的不同;温度对NO的生成特性也有明显的影响,基本随温度的升高而加大,但有时也有下降现象;生料的加入大大加速了NO的生成速率和转化率,表明生料对NO生成有显著的催化作用.工业分解炉中产生的NO主要来源于燃料NO,焦炭氮转化为NO的概率主要有两个互相竞争的反应决定：包括N的氧化反应和NO的还原反应.     

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.     

Fuel characteristics of wheat-based Dried Distillers Grains and Solubles (DDGS) for thermal conversion in power plants

For many years, the sole use of Dried Distillers Grains and Solubles (DDGS) has been as a feed for livestock, due to its high protein and fiber content. Recently there has been interest in DDGS as a power station fuel. In this study, DDGS produced from wheat has been studied for its fuel properties. Pyrolysis studies were conducted via Thermogravimetric Analysis (TGA) and pyrolysis gas chromatography-mass spectrometry (py GC-MS): the former was used to calculate the apparent first order kinetics while the latter helped to characterise pyrolysis products such as methoxyphenols and long chain fatty acids and esters. Fast heating rate chars were made, and nitrogen and sulphur partitioning between volatiles and chars are reported. In addition the chars were studied for their combustion behavior via Simultaneous Thermogravimetric Analysis with Mass Spectrometry detection (STA-MS) to study the conversion of char nitrogen and sulphur to different nitrogen and sulphur-containing species. In addition DDGS was combusted in a 50 kW fluid bed furnace, and the nitrogen species also monitored. DDGS is predicted to have a high alkali index that predicts high fouling tendency due to the high potassium and sodium contents in the ash. The phosphorus content in DDGS ash is also very high. Pyrolysis studies showed some oil evaporation/decomposition occurring at lower temperatures compared to decomposition of the lignocellulosic material. Nitrogen and sulphur partitioning showed that approximately 91% N and 94% S were given off as volatiles. The char was enriched with nitrogen but depleted in sulphur. Char combustion took place in two distinct stages indicating the presence of two types of chars, which yield selective evolution of S and N species during their combustion. Fluid bed combustion studies showed release of both HCN and ammonia during initial stages, when the bed is heating and the fuel undergoes devolatilisation. Steady-state combustion gave NO and N₂O emissions of 290 and 30 ppm respectively, with HCN and NH₃ emissions dropping to below 1 ppm. Agglomeration of the bed was avoided by keeping the combustion temperature below 900 °C     

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.     

The influence of mineral matters in coal on NO-char reaction in the presence of SO2

The effect of mineral matter in char on NO-char reaction in the presence of SO₂ was studied by temperature programmed reaction and isothermal experiments. Three coals with different ranks and their demineralized samples were pyrolyzed in N₂ at 900 °C to prepare the chars. Different kinds of metals were loaded on the demineralized chars to compare their catalytic effect on NO conversion during NO-char reaction. The results show that the effect of mineral matter is closely related to the content of catalytically active components. More catalytically active components in mineral matter in the char, higher catalytic activity for NO-char reaction. While the inert components, such as Al₂O₃ and Si₂O₃, will abate the NO conversion. Besides the catalytic effect of active mineral matter, the reactivity of the char is another important factor to affect the NO conversion during NO-char reaction. With increasing coal rank, the resultant char shows lower activity for reduction of NO. The effect of SO₂ on the NO-char reaction is changed with temperature. At higher temperatures NO conversion is further enhanced by the reaction of NO-SO₂ and the increase in the amount of active sites due to the release of SO₂ chemisorbed on the char surface.     

矿物质对煤焦燃烧过程中NO释放规律的影响

在石英固定床反应器上研究了煤焦燃烧过程中矿物质在不同燃烧条件下对NO释放规律的影响.结果表明：煤中的矿物质对燃料氮转化为NO有显著的影响,其影响与矿物质的组成和燃烧条件有关,碱金属Na、K催化半焦氮的氧化在较低的温度下进行并降低半焦氮对于NO的转化率,而Ca、Fe在低温燃烧条件下增加NO的排放,高温时使NO的排放降低;矿物质惰质组分的存在使NO的排放增加;随着煤阶的升高,半焦的反应性降低,燃料氮对于NO的转化率增大;燃料氮的转化率随燃烧温度的升高而增加,但达到极大值后又趋于降低;矿物质对于NO排放量的影响决定于矿物质对于半焦氮的氧化以及半焦还原NO反应催化作用的相对大小.     

Effect of rank,temperatures and inherent minerals on nitrogen emissions during coal pyrolysis in a fixed bed reactor

Pyrolysis of 11 coals with carbon contents of 77–93 wt.% (daf) and corresponding demineralized samples has been studied in a fixed bed quartz reactor with a heating rate of 20 K/min to examine rank, demineralization, temperature and inherent mineral species dependences of nitrogen distribution. Nitrogen mass balances fall within 92.5–104.6%. The results indicate that the chars derived from the coals with higher rank show larger nitrogen retention. Demineralization suppresses volatile nitrogen emission during coal pyrolysis, especially for low rank coals. Coal-N conversion to tar-N reaches the asymptotic values at 600 °C. HCN yields are lower than NH₃ yields during coal pyrolysis. The trends in HCN and NH₃ emissions are very similar and the yields reach the asymptotic value at about 1200 °C. N₂ starts emitting at 600 °C, and as the temperature increases the conversion increases linearly with a corresponding reverse change of char-N. With the catalysts added, N₂ formation is prompted with the sequence of Fe>Ca>K>Ti≫Na≫Si≈Al, meanwhile, char-N decreases correspondingly. Fe, Ca, K, Na, Si and Al increase coal-N conversion to NH₃ with the sequence of Fe>Ca>K≈Na≫Si≈Al in the pyrolysis. Na addition prompts HCN formation; however, the presence of Ti and Ca decrease the HCN yields with small value. The other catalysts have no notable influence on HCN emission in the pyrolysis. Demineralization and Ti addition increase coal-N conversion to tar-N slightly whereas K, Ca, Mg, Na, Si and Al additions decrease tar-N yield weakly, other catalysts hardly influence tar nitrogen emission. N₂ emits mainly from char-N with slight contribution of volatile nitrogen. The mechanism of different N-containing species formation and catalysts influence in the pyrolysis is also discussed in the paper.     

Change of nitrogen functionality of N-enriched condensation products during pyrolysis

Changes in the nitrogen functionality of ¹⁵N-enriched condensation products prepared from glucose and ¹⁵N-glycine were investigated during pyrolysis at 600–1000 °C. The structural changes in the condensation products were studied by means of solid-state ¹³C and ¹⁵N NMR spectroscopies. During pyrolysis, the aliphatic moieties of the condensation products decomposed and evolved as gas and tar. At pyrolysis temperatures above 600 °C, almost all the carbon in the chars were converted to aromatic carbon. After pyrolysis, large amounts of nitrogen remained in the chars as char nitrogen (char-N), and about 30% of the nitrogen was eliminated from the chars as HCN and NH₃. With increasing temperature, the production of HCN and NH₃ increased and the amount of char-N decreased. By combining X-ray photoelectron spectroscopy and NMR results, detailed results for nitrogen fractions in chars were obtained. During pyrolysis, the fraction of unsubstituted pyrrole-N decreased and the fraction of quaternary-N increased. The fraction of pyridine-N remained almost constant at temperatures below 800 °C, but at 900 °C and above, the fraction of pyridine-N decreased. The fraction of substituted pyrrole-N showed minimum at 800 °C. On the basis of these results, structural changes of nitrogen functional groups during pyrolysis are discussed.     

The catalytic steam gasification of chars from various sources by K2CO3

Gasification of a char prepared from hydrocracked residuum was compared with the gasification of chars prepared from bituminous and sub-bituminous Canadian coals, wood and graphite. Each material was mixed with 10 mass per cent K₂CO₃ and pyrolyzed up to 900°C. The yield of char was inversely proportional to the amount of volatile matter in the original material. The char prepared from hydrocracked residuum was different from the others. The other chars all followed zero-order gasification kinetics. Gasification of char prepared from the residuum was first-order in the solid. The development of a liquid phase during the pyrolysis of the residuum to char may explain this difference. The gasification rate of the char. from residuum was slower than the rates with the two coal chars and the wood char, but faster than the gasification rate of graphite. A combination of transient experiments and X-ray photoelectron spectroscopic (XPS) measurements indicated that hydrogen was formed almost instantaneously when steam reacted with the char. XPS spectra at liquid nitrogen temperature indicated that during gasification the formation of carbon oxygen bonds proceeded in the following sequence: COH, CO and CO.     

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.     

Coal devolatilization and char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of the present investigation is to examine differences between O₂/N₂ and O₂/CO₂ atmospheres during devolatilization and char conversion of a bituminous coal at conditions covering temperatures between 1173 K and 1673 K and inlet oxygen concentrations between 5 and 28 vol.%. The experiments have been carried out in an electrically heated entrained flow reactor that is designed to simulate the conditions in a suspension fired boiler. Coal devolatilized in N₂ and CO₂ atmospheres provided similar results regarding char morphology, char N₂-BET surface area and volatile yield. This strongly indicates that a shift from air to oxy-fuel combustion does not influence the devolatilization process significantly. Char combustion experiments yielded similar char conversion profiles when N₂ was replaced with CO₂ under conditions where combustion was primarily controlled by chemical kinetics. When char was burned at 1573 K and 1673 K a faster conversion was found in N₂ suggesting that the lower molecular diffusion coefficient of O₂ in CO₂ lowers the char conversion rate when external mass transfer influences combustion. The reaction of char with CO₂ was not observed to have an influence on char conversion rates at the applied experimental conditions.     

Structural analysis of chars generated from South African inertinite coals in a pipe-reactor combustion unit

An inertinite-rich medium rank C bituminous South African coal was utilized to generate chars in a pipe-reactor combustion unit. This unit generates chars at atmospheric pressures and temperature was controlled with N₂ to a maximum of 1250 °C. Chemical structural changes were investigated at different reaction zones identified in the pipe-reactor combustion unit. A combination of FTIR, XRD and Solid State NMR experiments were used to characterize the coal/char/ash fractions produced in the reactor. These techniques revealed that the coal structure becomes disordered in the drying zone as well as in the beginning of the pyrolysis zone in the reactor. As the temperature increases towards the base of the reactor the coal structure becomes more ordered and well aligned until char is formed and converted. Major structural changes were seen to occur in the drying to the pyrolysis zones. Structural changes within the molecular core were observed with FTIR and XRD results obtained from samples taken from the drying zone to the combustion zone. However, ¹³C CP/MAS and dipolar dephasing experiments were not able to corroborate these structural changes of the coal/char/ash fractions produced in the reactor occurring in the reduction and combustion zones.     

NH3 and HCN formation during the gasification of three rank-ordered coals in steam and oxygen

A Victorian brown coal (68.5% C), a Chinese high-volatile Shenmu bituminous coal (82.3% C) and a Chinese low-volatile Dongshan bituminous coal (90% C) were gasified in a fluidised-bed/fixed-bed reactor at 800 °C in atmospheres containing 15% H₂O, 2000 ppm O₂ or 15% H₂O + 2000 ppm O₂. While the gasification of these coals in 2000 ppm O₂ converted less than 27% of coal-N into NH₃, the introduction of steam played a vital role in converting a large proportion of coal-N into NH₃ by providing H on char surface. The importance of the roles of steam in the formation of NH₃ in atmospheres containing 15% H₂O + 2000 ppm O₂ decreased with increasing coal rank. This is largely due to the slow gasification of high-rank coal chars, resulting in low availability of H on char surface. The gasification of chars from the high-rank coal appears to produce higher yields of HCN than that of lower rank coals, probably as a result of the decomposition of partially hydrogenated/broken/activated char-N structures during gasification at high temperature. The alkali and alkaline earth metallic species in brown coal tend to favour the release of coal-N as tar-N but have limited effects on char-N conversion during gasification.     

An experimental investigation into the gasification reactivity of chars prepared at high temperatures

The gasification activities of three kinds of Binxian chars with carbon dioxide were studied at 1000–1300 °C and under atmospheric pressure in self-made thermal balance. The specific surface area of coal or chars was determined with BET methods during gasification. The results showed that the reaction rate of two rapid pyrolysis chars increases at the beginning and decreases subsequently with increasing carbon conversion at relatively high temperatures. The heating rate of coal has a significant effect on the gasification process. The activation energy of slow pyrolysis char varies between 160 kJ/mol and 180 kJ/mol during gasification. The activation energy of the two rapid pyrolysis chars displays a linear trend when the carbon conversion is less than 40% and decreases slowly afterwards.     

Combustion properties of some power station biomass fuels

In this study, the combustion properties of three of the UK’s commonly imported biomass fuels for co-firing, which are palm kernel expellers, shea residue, and waste from olive oil production are examined. The fuels were characterised and their thermal decomposition properties were studied by thermogravimetric analysis (TGA). Additionally the products from their devolatilisation were identified by gas chromatography-mass spectrometry (py-GC-MS) analysis of the evolved vapours and tars from high heating rate pyrolysis tests. Finally, chars from the fuels were prepared, analysed, and combustion studies were conducted by TGA-MS to determine the conversion of char-nitrogen to different nitrogen-containing species. In general, the main constituents of their ash fractions were K, Si, Ca and Mg, resulting in high alkali indices, which predict a large tendency to fouling. The pyrolysis and combustion kinetic parameters, estimated from TGA studies of these fuels and their chars, are much lower than those reported in the literature for lignocellulosic biomass. It is suspected that there is oil/fat evaporation processes overlapping with the decomposition of their lignocellulosic fractions, which significantly affects the apparent kinetics. The pyrolysis conditions used promoted depletion of nitrogen in the char, resulting in approximately 79-91% of the fuel-N being released with the volatiles. In combustion of the char, NO_x and N₂ are the major nitrogen compounds detected. Another primary product, HCN, was detected from the combustion of some of the fuel chars, as well as C₂N₂.     

Hydrogen production by methane cracking over different coal chars

Hydrogen production by methane cracking over a bed of different coal chars has been studied using a fixed bed reactor system operating at atmospheric pressure and 1123 K. The chars were prepared by pyrolysing four parent coals of different ranks, namely, Jincheng anthracite, Binxian bituminous coal, Xiaolongtan lignite and Shengli lignite, in nitrogen in the same fixed bed reactor operating at different pyrolysis temperatures and times. Hydrogen was the only gas-phase product detected with a GC during methane cracking. Both methane conversion and hydrogen yield decreased with increasing time on stream and pyrolysis temperature. The lower the coal rank, the greater the catalytic effect of the char. While the Shengli lignite char achieved the highest methane conversion and hydrogen yield in methane cracking amongst all chars prepared at pyrolysis temperature of 1173 K for 30 min, a higher catalytic activity was observed for the Xiaolongtan lignite char prepared at 973 K, indicating the importance of the nature of char surfaces. The catalytic activity of the coal chars were reduced by the carbon deposition. The coal chars had legible faces and sharp apertures before being subjected to methane cracking. The surfaces and pores of coal chars were covered with carbon deposits produced by methane cracking as evident in the SEM images. The results of BET surfaces areas of the coal chars revealed that the presence of micropores in the chars was not an exclusive reason for the catalytic effect of the chars in methane cracking.     

煤焦燃烧生成NO的特性研究

对小屯煤焦中氮的存在形态进行了X射线光电子能谱(XPS)分析。并对小屯煤焦在模拟分解炉中NO释放特性进行了实验研究,考察了气氛、温度、生料对焦炭氮释放特性的影响。研究结果表明:小屯煤焦中氮主要以吡咯五元环形式存在;氧气体积分数对NO的生成速率有明显影响;在无生料催化下,生成量基本随温度的升高而加大,但是,当生料存在时,生成量随温度的升高而减少;生料的加入大大加速了NO的生成速率和生成量,表明生料对NO生成有显著的催化作用。焦炭氮转化为NO的几率主要由2个互相竞争的反应决定:包括N的氧化反应和NO的还原反应。