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.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part VIII. Effects of pressure on the formation of NH3 and HCN during the pyrolysis and gasification of Victorian brown coal in steam

Effects of pressure on the formation of HCN and NH₃ during the pyrolysis and gasification of Loy Yang brown coal in steam were investigated using a pressurised drop-tube/fixed-bed reactor. The NH₃ yield increased with increasing pressure during both pyrolysis and gasification. Increasing pressure selectively favours the formation of NH₃ at the expenses of other N-containing species. The changes in the yield of NH₃ with increasing pressure were mainly observed in the feeding periods both during pyrolysis and gasification and were closely related to the formation and subsequent cracking of soot both as a result of intensified thermal cracking of volatile precursors inside the particles and as a result of volatile-char interactions after the release of volatiles. While the corresponding HCN yield during pyrolysis showed little sensitivity to changes in pressure, the HCN yield during gasification in steam showed some increases with increasing pressure. Our data indicate that the direct hydrogenation of char-N by H radicals, favoured by the presence of steam, is the main route of NH₃ formation during pyrolysis and gasification. The direct conversion, either through hydrogenation or hydrolysis, of HCN into NH₃ on char surface during the pyrolysis and gasification of brown coal is not an important route of NH₃ formation.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part VI. Effects of gas atmosphere on the formation of NH3 and HCN

Our results indicate that the gas atmosphere surrounding coal/char particles can greatly affect the formation of NH₃ and HCN through its influence on the availability of H radicals. Based on our results, it is believed that the chemisorption of CO₂ on the nascent char surface can consume H radicals or block the access of N-sites by H radicals for the formation of NH₃ and HCN. For the chars whose thermal cracking generates little H radicals, the gasification of char by CO₂ can also generate additional H radicals, enhancing the formation of NH₃. However, even gasification of char in CO₂ at 950 °C does not lead to the formation of HCN. The oxidation of coal with 4% O₂ at low temperatures (400-600 °C) leads to the formation of HCN as well as NH₃ due to the enhanced formation of (H) radicals. The gasification of coal with 15% H₂O drastically enhances the formation of NH₃ due to the greatly enhanced availability of H as an intermediate between the reactions of H₂O and char. These results support our reaction mechanisms proposed previously, emphasising the importance of H on the formation of NH₃ and HCN during pyrolysis, which can also be extended to the conversion of coal-N during gasification.     

Formation of HCN and NH3 during coal macerals pyrolysis and gasification with CO2

Three coal macerals with high purities were separated from Pingshuo gas coal. The formation rules of HCN and NH₃ during macerals pyrolysis and gasification were investigated. Experiments were carried out in a tubular quartz reactor at atmospheric pressure. The reactor allowed coal particles to be heated up rapidly and held for a prespecified period of time at a peak temperature. The amount of HCN and NH₃ were quantified by ion chromatography. The influence of temperature and macerals type on the formation rules of HCN and NH₃ was discussed. Results showed that the formation of HCN was mainly due to the thermal cracking of volatile, and NH₃ formed both from the thermal cracking of volatile and the cracking of nascent char. The HCN yield increased with an increase in pyrolysis temperature. For three coal macerals (liptinite, vitrinite and inertinite), the yield of HCN depended not only on their volatile contents but also nitrogen-containing functional groups, in which more pyrrole-type nitrogens would form more amount of HCN at lower temperature. The yield of NH₃ depended on the ability of forming ‘H’ radical. Under the experiment condition in this study, inertinite could convert more nitrogen into NH₃ than vitrinite and liptinite. The yield of HCN during gasification was almost the same as that during pyrolysis, the yield of NH₃ during gasification was little higher than that during pyrolysis.     

Formation of NOx precursors during wheat straw pyrolysis and gasification with O2 and CO2

The release behavior tests of NO_x precursors from wheat straw during pyrolysis in argon and gasification in 5%O₂/95%Ar and 5%CO₂/95%Ar were performed using a thermogravimetric analyzer (TGA) coupled with a Fourier transform infrared (FTIR) spectrometer. The results show that heating rate and particle size have substantial effects on the selectivity of N-conversion due to the selectivity of cracking of cyclic amides and the secondary reaction influencing the formation of NH₃, HCN and HNCO. The atmosphere influences the N-selectivity to HCN, NH₃, NO and HNCO. The formation of HCN and NH₃ in 5%O₂/95%Ar is a result of competition among the opposing effects of O₂. The presence of O₂ promotes the yields of HCN and HNCO evidently, and HNCO seems to be a favourable product from biomass-N compared in Ar atmosphere although HCN yield is a little bigger than that of HNCO. The use of CO₂ reduces the formation of HCN, the yield of NH₃ keeps essentially constant compared in Ar, and the emission of HNCO is suppressed. NH₃ seems to be a favourable product from biomass-N in 5%CO₂/95%Ar.     

Formation of NOx and SOx precursors during the pyrolysis of coal and biomass. Part IV. Pyrolysis of a set of Australian and Chinese coals

The formation of HCN and NH₃ from the pyrolysis of a small set of Chinese and Australian coals were studied using a novel fluidised-bed/fixed-bed reactor and a fluidised-bed/tubular reactor. The fluidised-bed/fixed-bed reactor has some features of a fluidised-bed reactor and of a fixed-bed reactor, allowing the evaluation of the effects of coal properties on the formation of HCN and NH₃ to be carried out on a similar basis for a wide range of coals. The thermal cracking of volatiles was investigated in a tubular reactor in tandem with the fluidised-bed/fixed-bed reactor where the nascent volatiles were generated in situ from the pyrolysis of coal. Our experimental results indicate that, in addition to coal rank, the petrographic composition and/or geographic origin of the coal are important factors influencing the formation of HCN and NH₃ during pyrolysis. Among the few Chinese and Australian coals studied, the inertinite-rich Chinese coals tend to give more NH₃ during pyrolysis than the Australian coals of similar carbon contents. It is believed that the structure of inertinites of less caking properties favours the formation of H radicals in the pyrolysing solid over a ‘correct’ temperature range to overlap with the activation and subsequent hydrogenation of the N-containing ring systems for the formation of NH₃ in the solid. If the coal properties favour the release of coal-N as volatiles, the formation of HCN in the gas phase is more likely. Under the current experimental conditions, where volatiles may be deposited on the reactor wall, the formation and destruction of the sooty materials on the reactor wall play an important role in the formation of HCN from the cracking of volatiles.     

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.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part X: Effects of volatile-char interactions on the conversion of coal-N during the gasification of a Victorian brown coal in O2 and steam at 800 °C

A novel fluidised-bed/fixed-bed reactor was used to study the effects of volatile-char interactions on the conversion of coal-N during the gasification of a Victorian brown coal at 800 °C. The reactor has the capability of controlling the extent and length of the interactions between volatiles and char. Our results indicate that in the absence of volatile-char interactions during gasification in O₂, the lack of abundant H radicals led to negligible formation of NH₃ and HCN from char-N. The presence of volatile-char interactions during the gasification of Victorian brown coal in O₂ at 800 °C drastically enhanced the formation of NH₃ and, albeit to a lesser extent, the formation of HCN. The enhanced conversion of char-N into NH₃ (and HCN) due to the volatile-char interactions is attributed to the presence of H radicals in the volatiles. H radicals in volatiles could “die off” as they pass through the nascent char bed during the course of volatile-char interactions.     

NOx precursors evolution during coal heating process in CO2 atmosphere

The pyrolysis/gasification experiments of Xuzhou bituminous coal (XZ) and Longyan anthracite (LY) were carried out in a tube furnace under Ar or CO₂ atmosphere, and the effect of CO₂ on the evolution of NO_x precursors, NH₃ and HCN, was studied using a Fourier transform infrared (FTIR) spectrometer. Results show that CO₂ influences NH₃ and HCN evolution process in two main ways: one is blocking the contact of the N-sites and the H-radicals by absorbed on the coal matrix surface at low temperature, and the other is opening the N-sites from the coal matrix by gasification at high temperature. For both XZ and LY coals, CO₂ atmosphere suppresses NH₃ yield and enhances HCN yield due to the gasification effect compared with that in Ar atmosphere. But the impact is not the same. The HCN/NH₃ ratio is elevated in CO₂ atmosphere compared with that in Ar atmosphere.     

Effects of volatile–char interaction on the formation of HCN and NH3 during the gasification of Victorian brown coal in O2 at 500 °C

In a coal gasifier interactions between volatiles and char are significant. The partly reducing conditions in a gasifier would mean the presence of high concentration of partial oxidation products and radicals surrounding the char particles. Currently, little is known about the effects of in situ volatile–char interactions on the conversion of char-N. This study examines the effect of in situ volatile–char interactions on the formation of HCN and NH₃ during the low temperature (500 °C) gasification of Loy Yang brown coal in oxygen. Two novel reactor systems were used. The reactor configurations allowed the quantification of HCN and NH₃ from char-N gasification, volatile-N oxidation and volatile–char interactions separately. Our results indicate that volatile–char interactions can have drastic effects on coal-N conversion during gasification by providing an important source of the radicals for the formation of HCN and NH₃ from char-N during gasification in 4% or 8% O₂ at 500 °C. In the presence of radicals and O₂, N-containing structures in the nascent char can be easily broken down to give HCN and NH₃ during the gasification of the char. In the absence of O₂, some of the nascent char-N structures may stabilise into structures less favourable for the formation of HCN and NH₃ and more favourable for the formation of other N-containing species such as NO_x.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part IX. Effects of coal ash and externally loaded-Na on fuel-N conversion during the reforming of coal and biomass in steam

Ash interacts strongly with char and volatiles in a gasifier, especially in a fluidised-bed gasifier. This study aims to investigate the effects of ash or ash-forming species on the conversion of fuel-N during gasification. A Victorian (Loy Yang) brown coal and a sugar cane trash were gasified in two novel fluidised-bed/fixed-bed reactors where the interactions of ash with char and/or volatiles could be selectively investigated. Our results show that the interaction of ash with char and/or volatiles could lead to increases in the yield of NH₃ and decreases in the yield of HCN although the increases were not always matched exactly by the decreases. Loading NaCl or Na₂CO₃ into the brown coal was also found to affect the formation of HCN and NH₃ during gasification. In addition to the possible catalytic hydrolysis of HCN into NH₃ particularly at high temperatures, two other causes were identified for the changes in the HCN and NH₃ yields. It is believed that some ash species could migrate into the char matrix to affect the local availability of H radicals or to catalyse the formation of NH₃ selectively. The interactions of ash (or Na loaded into the coal) with volatiles could enhance the formation of soot-N, which would be gasified favourably to form NH₃.     

Formation of N-containing gas-phase species from char gasification in steam

The formation of N-containing products during char-steam gasification has been investigated in a laboratory scale fixed bed reactor. Experiments were conducted at 1000 °C, 0.1-1.0 MPa, and 6-46% of H₂O in He base flow. Two very different coal chars, which were prepared from the rapid heating of Australian bituminous and sub-bituminous coals, were studied. The nitrogen-containing products released during the gasification were measured using an FTIR spectrometer (NH₃, HCN and HNCO) and gas chromatography (N₂). The major N-containing products formed during char-steam gasification are NH₃, HCN and N₂. Reactions of HCN in the same reactor were also studied; these experiments were conducted with HCN alone, HCN/steam, and HCN/steam/char. The results are consistent with a mechanism in which HCN is the primary N-containing product of the char-steam reaction, and the additional products result from further reactions of HCN either in the gas phase or promoted by the surface of the reactor or the char. Increasing concentrations of steam significantly influence the distribution of char-N to N-containing gas-phase products, resulting in the increase of NH₃ at the expense of N₂. Some differences in char behaviour are also observed, particularly on the distribution of N-containing products at 0.1 MPa total pressure.     

Formation of NOx and SOx precursors during the pyrolysis of coal and biomass. Part I. Effects of reactor configuration on the determined yields of HCN and NH3 during pyrolysis

The formation of HCN and NH₃ during the pyrolysis of a biomass (bagasse) and a set of rank-ordered coal samples has been studied in a novel reactor. The reactor has some features of both a drop-tube reactor and a fixed-bed reactor: the reactor allows the coal/biomass particles to be heated up rapidly as well as to be held for a pre-specified period of time at peak temperature. The experimental results obtained suggest that a considerable amount of the nitrogen in the nascent char could be converted into HCN and NH₃ if the char is held at high temperatures for long time. The formation of NH₃ from the thermal cracking of char was seen to last for more than an hour even at temperatures as high as 700–900°C. The formation of HCN went to completion much more rapidly than that of NH₃. Compared with the results in the literature from the pyrolysis of coals in a fluidised-bed reactor, the reactor configuration used in this study allows the effects of fuel rank to be studied on an unbiased basis towards the type of fuel. The yields of HCN and NH₃ from the present study decrease with increasing rank. The experimental results suggest that the differences in reactor configurations used by various researchers would account at least partially for some of the discrepancies in the literature regarding the formation of HCN and NH₃ during the pyrolysis of coals.     

Nitrogen chemistry in coal pyrolysis: Catalytic roles of metal cations in secondary reactions of volatile nitrogen and char nitrogen

The present review focuses on elucidating the chemistry of nitrogen release during coal pyrolysis, in particular, on making clear catalytic roles of inherent Ca and Fe ions in not only the partitioning of volatile-N to tar-N, HCN, NH₃ and N₂ but also the conversion of char-N to N₂.     

Experimental investigation of nitrogen species release from different solid biomass fuels as a basis for release models

Experimental data on the release of NO_x precursors from solid biomass fuels during thermal conversion are necessary to study N release in general and to supply reliable data for the purpose of packed bed and gas phase conversion model development and validation. In this work the release of NO_x precursors was studied at a lab-scale pot furnace (batch reactor) by taking measurements during the conversion process of solid biomass in a packed bed. The investigations were carried out with relevant woody biomass fuels, which cover a broad range of fuel N contents: sawdust, bark, waste wood and MDF board. The most important NO_x precursor detected above the fuel bed under fuel rich conditions was NH₃, while HCN was almost insignificant with the exception of sawdust. NO was detected mainly under air rich conditions. Furthermore, the experimental data were utilised to derive release functions for the relevant NO_x precursors NO, NH₃ and HCN. The release functions were implemented in an in-house empirical packed bed combustion model, which serves as a basis for a subsequent CFD N species gas phase calculation.     

Pyrolysis of poly-l-leucine under combustion-like conditions

The protein poly-l-leucine has been used as a model compound for the nitrogen in biomass fuels. It was pyrolysed in a fluidised bed at 700 and 800 °C and the pyrolysis gases were analysed with a FT-IR spectrometer. HCN, NH₃ and HNCO were identified as the main nitrogen-containing species, while neither NO nor N₂O were found among the pyrolysis gases. At 700 °C, as much as 58% of the nitrogen content was converted into HCN and 31% into NH₃. The HCN/NH₃ ratio increased from about 1.9 at 700 °C to above 2.2 at 800 °C. Pyrolysis of another protein, poly-l-proline, at 800 °C gave a HCN/NH₃ ratio close to 10. This revealed that the protein's amino acid composition has a marked impact on the composition of the pyrolysate.     

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.     

Loy Yang褐煤热解过程中HCN和NH3形成的主要影响因素

引　言热解是煤燃烧和气化的初始步骤 ,作为煤有机成分之一的N在煤热解过程中将随挥发分的释放而转化为NH3、HCN和少量的HNCO等气态NOx 前驱物、N2 以及焦油N和焦N[1,2 ] ,这些NOx 前驱物及焦N在后续的燃烧、气化过程中将转化为NOx/N2 O或者N2 [3,4 ] .煤燃烧过程中释放的NOx/N     

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.     

流化床煤燃烧过程不同气氛下的气态氮释放特征

利用微型流化床反应装置,结合快速过程质谱仪,在850~940℃操作温度下,研究了三种不同粒度分布烟煤和无烟煤在热解、气化和燃烧反应条件下四种主要气态氮产物HCN、NH₃、NO和NO₂的释放规律。结果表明,微型流化床可以实时检测挥发分氮和焦炭氮的动态释放序和类型,热解、气化和燃烧反应气氛的改变主要影响HCN和NH₃的释放量。热解产物的气态氮主要是来自于挥发分,燃烧反应的HCN和NH₃的释放量与温度有明显关系,而气化反应的各类气态氮释放量随温度变化波动不大。煤颗粒尺寸和温度变化对烟煤和无烟煤中各类气态氮释放量产生影响比较复杂,其中NH₃的释放特性是区分挥发分N释放和半焦N释放的重要特征。