Computer-controlled scanning electron microscopy of minerals in coal-Implications for ash deposition

The nature of mineral matter in coal determines its transformation into ash during combustion and the nature of resulting ash (e.g. chemical composition and particle size distribution), and subsequently influences the ash deposition behaviour. The behaviour of mineral matter is primarily influenced by two parameters: the mineral grain size, and whether the mineral grains are within the coal matrix or not. Computer-controlled scanning electron microscopy (CCSEM) of coal provides such information on mineral matter in coal. CCSEM data are, therefore, processed to predict the fouling and slagging characteristics of several coals. The fraction of basic oxides in each mineral grain may be considered as an indicator of stickiness of the corresponding ash particle due to formation of low melting compounds. The cumulative mass fraction of mineral grains with certain basic oxides or viscosity of resulting ash particles from included and excluded minerals are proposed as alternative indices for ash deposition.

The excluded mineral matter is in equilibrium with the combustion flue gases at the gas temperatures, whereas the included minerals are in equilibrium with the atmosphere within char at the burning char particle temperature. It is predicted from thermodynamic calculations based on this understanding that almost all the evaporation is either from the included mineral matter or from the atomically dispersed minerals in coal. This is due to the high temperature and reducing atmosphere inside the char particle. The release of the evaporated species is controlled by diffusion through the burning char particle and, therefore, may be estimated theoretically. The amount of mineral matter that is vaporized may then be related to fouling, whereas the melt phase present on the surface of large ash particles may be related to slagging. The theoretical speculations on the physical character of ash derived from these indices are compared with the experimental data obtained from combustion of coals in a drop-tube furnace.     

Factors influencing the transformation of minerals during pulverized coal combustion

The transformation of minerals and dispersed inorganic constitutents during pulverized coal combustion has been examined by burning utility sized coals (70% less than 200 mesh) in a laboratory-scale combustor. Experiments were conducted with four U.S. coals possessing different mineralogies. Size and composition of the initial minerals and the resulting ash were measured by a variety of techniques, including computer controlled SEM, low temperature ashing, deposition on a cascade impactor, and optical (Malvern) particle size analysis. Results for a Kentucky # 11 coal with a large amount of fine, included silicate minerals suggest that coalescence amongst illite, kaolinite, and quartz minerals was the dominant process, with occasional iron incorporation into the resulting glass. Pyrite was found to fragment to a limited extent. Illinois # 6 bituminous coal, possessing a similar mineralogy, yielded similar results. For a Beulah lignite coal containing large pyrite grains, mineral fragmentation was inferred from the data, increasing with increasing oxygen level. A high ash content San Miguel Texas lignite containing zeolite minerals demonstrated little mineral interaction during combustion. Differences in results obtained for the different coals highlighted the importance of understanding individual mineral transformations in predicting the formation and behavior of ash.     

Distribution of mineral matter in pulverized coal

Mineral transformations, and therefore fly ash evolution, during pulverized coal combustion, depend on the amount, composition and spatial distribution of the inorganic matter within individual pulverized coal particles. Thus, it is necessary to have information on the mineral composition of individual particles, as well as that of the raw pulverized coal. A model is proposed based on the assumption that mineral inclusions of size and composition determined using a CCSEM are distributed randomly in the coal. From this distribution it is possible to generate distributions of mineral content for any particle size and density fraction of coal. The model has been checked by comparing computed results with data on the compositional variations of narrowly and density classified fractions of an Upper Freeport bituminous coal. The results of individual coal particle compositions are used to generate information on the variability of the composition of the fly ash generated during combustion.     

Studies of transformations of inorganic constituents in a Texas lignite during combustion

The mechanisms of coal ash formation were studied under closely controlled combustion conditions. Monticello lignite, from Titus County, Texas was combusted in a drop-tube furnace at 1500°C and fly ash was collected and aerodynamically size segregated into six stages. Short residence time chars were also produced in the drop-tube furnace. The coal was analyzed to determine both mineralogical and organically bound components using computer controlled scanning electron microscopy (CCSEM) and chemical fractionation techniques, respectively. Scanning electron microscopy/microprobe techniques were used to classify and determine the distribution of various ash particle types in each size fraction. Over 80% of the Monticello mineral content consisted of quartz and clay minerals and relatively large quantities of Ca, Mg, and possibly Fe were organically bound. Extensive reaction between the quartz and clay minerals and organically bound Ca resulted in amorphous and crystalline Ca-silicate and Ca-aluminosilicate phases in the fly ash. Finely subdivided discrete minerals or organically bound cations of Mg and Fe were concentrated in the finer fraction of the fly ash.     

基于灰颗粒的物理特性为分类原则的试验研究

循环流化床(CFB)锅炉炉内的燃烧及传热与炉内床料的状态密切相关,而炉内床料主要是由燃煤含有的矿物组分经过燃烧、爆裂和磨耗过程形成的。文中对6种煤样在固定床燃烧后,使用可视化显微仪,获取了灰颗粒的微观形貌特征,根据灰颗粒的机械强度和耐磨性能的不同,将灰颗粒定义为3类不同性质的灰。以此为基点,采用固定床燃烧后冷态振动筛分和流化床实验台热态流化后筛分的方法,研究了不同燃烧温度下升温速率对灰颗粒粒径变化的影响,以及不同燃烧温度下燃烧时间对灰颗粒粒径变化的影响,推演了不同煤样在燃烧过程中的演化特征。结果表明:3类灰颗粒在不同的燃烧温度和时间的演化过程存在明显的不同,从而为预测循环流化床中的床料粒径分布提供了理论依据。     

Experimental studies of ash film fractions based on measurement of cenospheres geometry in pulverized coal combustion

In pulverized coal particle combustion, part of the ash forms the ash film and exerts an inhibitory influence on combustion by impeding the diffusion of oxygen to the encapsulated char core, while part of the ash diffuses toward the char core. Despite the considerable ash effects on combustion, the fraction of ash film still remains unclear. However, the research of the properties of cenospheres can be an appropriate choice for the fraction determination, being aware that the formation of cenospheres is based on the model of coal particles with the visco-plastic ash film and a solid core. The fraction of ash film X is the ratio of the measuring mass of ash film and the total ash in coal particle. In this paper, the Huangling bituminous coal with different sizes was burnt in a drop-tube furnace at 1273, 1473, and 1673 K with air as oxidizer. A scanning electron microscope (SEM) and cross-section analysis have been used to study the geometry of the collected cenospheres and the effects of combustion parameters on the fraction of ash film. The results show that the ash film fraction increases with increasing temperature and carbon conversion ratio but decreases with larger sizes of coal particles. The high fraction of ash film provides a reasonable explanation for the extinction event at the late burnout stage. The varied values of ash film fractions under different conditions during the dynamic combustion process are necessary for further development of kinetic models.     

Mineral behavior during coal combustion 1. Pyrite transformations

The transformations and deposition characteristics of pyrite (FeS₂) under pulverized coal combustion conditions were examined in an entrained flow reactor. Mössbauer spectroscopy, scanning electron microscopy, and energy dispersive X-ray analysis, were used to monitor the evolution of particle composition and morphology. Pyrite initially decomposed to form pyrrhotite (Fe_0.877S). Fissures resulting within the particle during this step led to limited bulk fragmentation. Subsequently, the pyrrhotite particles melted to form an iron oxysulfide droplet. Magnetite (Fe₃O₄) crystallized out of the melt once the melt oxide content exceeded 85%. Hematite (Fe₂O₃) was formed at longer residence times. A comparison of kinetic model calculations with experimental data revealed the controlling resistances for each of the stages during the transformation process. Deposition experiments established the iron oxysulfide phase to be responsible for particle adhesion, and the duration of this melt phase was determined to be a function of pyrite particle size, gas temperature, oxygen concentration, and the extent of fragmentation. Combustion experiments were also conducted with two coals, one with predominantly included pyrite grains and the other with a significant fraction of excluded pyrite, to discern the limiting behavior of pyrite in forming the final ash.     

Effect of temperature on Lu’an bituminous char structure evolution in pyrolysis and combustion

In the process of pyrolysis and combustion of coal particles, coal structure evolution will be affected by the ash behavior, which will further affect the char reactivity, especially in the ash melting temperature zone. Lu’an bituminous char and ash samples were prepared at the N₂ and air atmospheres respectively across ash melting temperature. A scanning electron microscope (SEM) was used to observe the morphology of char and ash. The specific surface area (SSA) analyzer and thermogravimetric analyzer were respectively adopted to obtain the pore structure characteristics of the coal chars and combustion parameters. Besides, an X-ray diffractometer (XRD) was applied to investigate the graphitization degree of coal chars prepared at different pyrolysis temperatures. The SEM results indicated that the number density and physical dimension of ash spheres exuded from the char particles both gradually increased with the increasing temperature, thus the coalescence of ash spheres could be observed obviously above 1100°C. Some flocculent materials appeared on the surface of the char particles at 1300°C, and it could be speculated that β-Si₃N₄ was generated in the pyrolysis process under N₂. The SSA of the chars decreased with the increasing pyrolysis temperature. Inside the char particles, the micropore area and its proportion in the SSA also declined as the pyrolysis temperature increased. Furthermore, the constantly increasing pyrolysis temperature also caused the reactivity of char decrease, which is consistent with the results obtained by XRD. The higher combustion temperature resulted in the lower porosity and more fragments of the ash.     

Particulate matter emission and K/S/Cl transformation during biomass combustion in an entrained flow reactor

This study aims to demonstrate the effect of ash chemistry, especially, the transformation of potassium (K), chlorine (Cl), and sulfur (S) species, on the fine particle emission during biomass combustion. Biomass was burned in an entrained flow reactor at varied temperature from 1000 to 1300 °C, where fine particles were sampled using a 13-stage low pressure impactor, and the morphology and composition of the fine particles were analyzed. The fates of K, Cl, and S during biomass combustion were compared between the entrained flow reactor and the muffle furnace. Results show that the particle size distributions of PM₁₀ are bimodal for all studied cases. A higher concentration of fine-mode particle is observed at 1000 °C, with the peak position at 0.274 μm. When the temperature is increased from 1000 to 1100 °C or higher, the concentration of fine-mode particle is reduced by about 50%, and its size becomes smaller with a peak position at 0.097 μm. K, Cl and S are enriched as potassium chloride and sulfate, dominantly in PM_1.0; while Mg, Ca and Si are enriched in PM_1.0–10. A certain amount of sulfur in PM_1.0 at 1000 °C is observed, while the sulfur disappears above 1100 °C. This indicates that the process of potassium sulfation tends to occur at a moderate temperature, and affects the emission amount and the particle size distribution of particulate matters. Analyzing results of the fates of K, Cl and S in the particle phase indicate a completed sulfur-release from biomass ash above 1200 °C, as well as a maximum capture efficiency for potassium-containing vapors at 1100 °C, which results in a minimum PM_1.0 emission at 1100 °C.     

Optimizing a woodchip and coal co-firing retrofit for a power utility boiler using CFD

A computational fluid dynamics (CFD) tool, CFX-TASCflow, with a drag force sub-model for woodchip particles was used to explore the optimization of woodchip co-firing of a Canadian utility boiler, after it was first validated by comparing the model results with field operation data when firing Colombia coal. The CFD model predicted both a small increase in NO emissions and a significant increase in unburned carbon in fly ash for the originally proposed co-firing configuration, with 85% of the unburned carbon originating from the woodchips. Improvement strategies were examined, including intensifying the swirl inside the furnace to improve oxygen availability for woodchip combustion, lowering the woodchip injection level to increase residence time, and reducing woodchip particle size to shorten burnout time. The model results revealed the importance of intensified swirl on the burnout of large woodchip particles and the sensitivity of NO emissions to the air distribution in the combustion zone. Also, the model predicted an increase in large unburned woodchip particles falling into the bottom hopper when lowering woodchip injection level, although there was an overall improvement in predicted woodchip burnout. An improvement in woodchip burnout was also observed with reduced woodchip particle size. Based on these results, a co-firing strategy is suggested that is predicted to give reasonable burnout and NOx emissions at a minimum retrofitting cost.     

煤飞灰中砷的形态特性

对某 3 0 0MW燃煤电厂锅炉进行煤、渣、飞灰取样后 ,测定煤和燃烧产物中砷的含量 ,计算了砷在燃烧产物中的分布 ,研究了电除尘 4个电场飞灰中砷含量与粒径的关系 .结果表明 ,通过除尘装置滞留下来的砷量占总砷量的 5 1.8% .飞灰中砷的含量随着粒度的降低而升高 .使用逐级化学浸提法研究了粒度不同的飞灰中砷的形态分布 .将飞灰中的砷分为水可浸出态、可交换态、碳酸盐 表面氧化物结合态、铁锰氧化物结合态以及残渣态 .不同粒径的飞灰形态分布相似 ,即残渣态 >碳酸盐 表面氧化物结合态 >铁锰氧化物结合态 >可交换态     

Effect of reactivity loss on apparent reaction order of burning char particles

Considerable debate still exists in the char combustion community over the expected and observed reaction orders of carbon reacting with oxygen. In particular, very low values of the reaction order (approaching zero) are commonly observed in char combustion experiments. These observations appear to conflict with porous catalyst theory as first expressed by Thiele, which suggests that the apparent reaction order must be greater than 0.5. In this work, we propose that this conflict may be resolved by considering the decrease in char reactivity with burnout due to ash effects, thermal annealing, or other phenomena. Specifically, the influence of ash dilution of the available surface area on the apparent reaction order is explored. Equations describing the ash dilution effect are combined with a model for particle burnout based on single-film nth-order Arrhenius char combustion and yield an analytical expression for the effective reaction order. When this expression is applied for experimental conditions reflecting combustion of individual pulverized coal particles in an entrained flow reactor, the apparent reaction order is shown to be lower than the inherent char matrix reaction order, even for negligible extents of char conversion. As char conversion proceeds and approaches completion, the apparent reaction order drops precipitously past zero to negative values. Conversely, the inclusion of the ash dilution model has little effect on the char conversion profile or char particle temperature until significant burnout has occurred. Taken together, these results suggest that the common experimental observation of low apparent reaction orders during char combustion is a consequence of the lack of explicit modeling of the decrease in char reactivity with burnout.     

锅炉燃煤方式对痕量元素分布的影响

综述了目前国内外锅炉燃烧方式对痕量元素分布的影响。测定了我国5台不同炉型和容量的工业锅炉底灰和飞灰中痕量元素的分布情况,结果表明：流化床燃烧时煤中痕量挥发性元素的蒸发较大;不易挥发痕量元素的分布不受炉型的影响;工业锅炉容量增大时,痕量元素在细颗粒上富集;飞灰颗粒越小,富集越多。     

无烟煤流化床燃烧中热破碎现象的研究综述

归纳用于衡量破碎程度的参数,分析产生破碎的机理,研究影响热破碎的因素,讨论破碎现象对燃烧的作用。总结认为。流化床燃烧中。无烟煤的破碎具有较大随机性,受煤质影响极大,粒径、炉床温度、停留时间、流化介质及流化速度等对破碎也有重要影响。煤的破碎有利于提高煤焦颗粒的燃烧速率,但同时也会增加炉床内可扬析颗粒数量,导致飞灰未燃碳含量增加的后果。实现破碎物料的准确快速取样和建立破碎前后颗粒平均粒径之间的关系是今后破碎研究工作尚待解决的问题。     

Modeling the behavior of selenium in Pulverized-Coal Combustion systems

The behavior of Se during coal combustion is different from other trace metals because of the high degree of vaporization and high vapor pressures of the oxide (SeO₂) in coal flue gas. In a coal-fired boiler, these gaseous oxides are absorbed on the fly ash surface in the convective section by a chemical reaction. The composition of the fly ash (and of the parent coal) as well as the time-temperature history in the boiler therefore influences the formation of selenium compounds on the surface of the fly ash. A model was created for interactions between selenium and fly ash post-combustion. The reaction mechanism assumed that iron reacts with selenium at temperatures above 1200 °C and that calcium reacts with selenium at temperatures less than 800 °C. The model also included competing reactions of SO₂ with calcium and iron in the ash. Predicted selenium distributions in fly ash (concentration versus particle size) were compared against measurements from pilot-scale experiments for combustion of six coals, four bituminous and two low-rank coals. The model predicted the selenium distribution in the fly ash from the pilot-scale experiments reasonably well for six coals of different compositions.     

Combustion characteristics of GAP-coated boron particles and the fuel-rich solid propellant

A process was employed that permits the coating of energetic glycidyl azide polymer (GAP) on the boron surface. Ignition and combustion behavior of single particle pure crystalline boron and GAP-coated boron at atmospheric pressure was studied experimentally by injecting the particles into the stream of hot gaseous environment of a flat-flame burner using premixed propane-oxygen-nitrogen gases. Chopped streak photographic observation was used to measure the ignition and combustion time. The flame temperature was fixed around 2343 K, but under wider O₂ level range than previous investigations. Measurement results show that GAP coating can shorten boron particle ignition delay time, however, the effect diminishes as the O₂ level in combustion gas decreases. Possible mechanisms based on relevant reactions and heat effects were proposed. Combustion characteristics of fuel-rich solid propellants based on GAP-coated amorphous boron particles and uncoated ones were compared using different techniques such as combustion phenomena observations by a windowed strand burner, quenched propellant surface morphology analysis by scanning electron microscope, and combustion residues size analysis from the quenched particle collection bomb experiments. It was concluded that GAP-coated amorphous-boron-based fuel-rich propellants exhibit more vigorous combustion phenomena, higher burning rates, and a lesser extent of residue agglomeration than the uncoated baseline propellant. Moreover, reaction mechanisms were proposed to elucidate the combustion products obtained in this study.     

Effects of oxy-fuel condition on morphology and mineral composition of ash deposit during combustion of Zhundong high-alkali coal

Zhundong coalfield is a super-large coal reserve, with high-alkali feature exacerbating ash deposition. Oxy-fuel combustion technology could propel the clean utilization of Zhundong high-alkali coal. While the ash deposition behavior of high-alkali coal under oxy-fuel condition has yet to be sufficiently investigated. The present study compared the differences of ash deposits between oxy-fuel and air combustion, and also examined the effects of oxygen content on ash deposition mechanism, employing a drop-tube furnace equipped with a specially designed sampling probe and some analysis methods, such as X—ray diffraction equipment, simultaneous thermal analyzer, etc. Experimental results indicated that ash deposition was weaker, with fewer contents of sodium chloride, calcium sulphate and less agglomeration ash in oxy-fuel atmosphere compared to the air case with same oxygen content. The content of the ash particle distributed in the range of 0–40 μm was up to 60% under oxy-fuel condition. The first weight loss of ash deposits, around 850 °C, was put down to the decomposition of carbonate and the second one, about 1150 °C, was ascribed to the decomposition of the sulphate minerals in the thermal process. Ash deposition worsened with more large particles (>120 μm), as the oxygen content rose. Sodium chloride content reached 9.7% with 50% oxygen content. The present study not only focuses on the morphology and chemical components, but also probes into the thermal volatility of ash deposits, which benefits the further understanding of the ash deposition mechanism and utilization of Zhundong high-alkali coal during oxy-fuel combustion.     

Experimental investigation of the two-phase theory in a fluidized-bed combustor

Though the two-phase theory of fluidization is well-accepted, no direct experimental measurements of the different gas concentrations predicted to occur in bubble and particulate phases could be found in the literature. For the first time, theoretical predictions of these different gas concentrations have been validated experimentally, using a combined oxygen/bubble probe. Based on the two-phase theory, a mathematical model was developed for the combustion of a batch of char particles in a fluidized-bed combustor. The experimental oxygen concentration in the particulate phase as a function of time was well predicted by the model. Slight discrepancies for the bubble phase values were eliminated when low-oxygen-concentration bubbles were excluded from the data, attributed to some char combustion occurring in bubbles being contrary to the model assumption. The temperature difference between char and bed particles (ΔT) was the only adjustable parameter in the model. A value of 20°C fitted the burnoff times measured by visual observation of the top of the bed, for both 5 and 10 g char batch masses. Model predictions of the oxygen concentrations were not sensitive to ΔT during the first half of burnoff, when mass transfer controlled the combustion rate, so the mass transfer processes were predicted correctly by the model effectively with no adjustable parameter. The ΔT value of 20°C was significantly lower than experimental measurements of maximum burning char particle temperatures, reported to be 70°C for the small-diameter bed particles used in this work. The discrepancy was attributed to two factors: (i) the decrease in char particle temperature towards the end of the burnoff, when kinetics significantly affected the combustion rate; and (ii) a lower char particle temperature in the particulate phase than in the bubble phase, with experimental char particle temperature measurements biased towards the higher bubble phase values. It was inferred: (i) that the maximum values of ΔT measured experimentally are too high for calculation of the char particle combustion rate during the kinetic-controlled latter stage of burnoff and (ii) that reported values of the heat transfer coefficient from burning char particles to the particulate phase deduced from these particle temperature measurements may have been underestimated.     

Ignition and combustion of boron particles

The successful development of highly energetic boron-based propellants will require a thorough knowledge of the chemical and physical processes controlling ignition and combustion of single boron particles. Significant recent progress on various problems in the field of boron particle combustion makes our goal prospective.

This paper reviews our current understanding of the ignition and combustion processes of single boron particles, including a comprehensive survey of the previous experimental work, theoretical models, and chemical kinetics studies. In addition, this paper presents up-to-date research findings which represent two major research needs strongly recommended by previous researchers.

An experimental diagnostics was developed to study the ignition and combustion of fine-size single particles. The measured ignition delay and two-stage combustion times of single boron particles with sizes of 3 μm are presented. Effects of gas temperature, oxygen concentration, and magnesium coating on boron combustion were examined.

An investigation was performed to resolve long-term contradicting theories regarding the mechanisms which governed the species diffusion across the liquid B₂O₃ layer covering a single boron particle at elevated temperatures. Observations showed that the diffusion of dissolved boron into molten B₂O₃₍₁₎ dominates the diffusion process through the liquid layer. Subsequently, a polymeric vitreous (BO)_n complex is formed through the reaction between dissolved boron and molten B₂O₃₍₁₎. Based upon these experimental findings, an appropriate boron reaction mechanism was obtained by deduction. A theoretical model was then developed to simulate boron particle combustion in two consecutive stages.     

Investigation on the effects of fly ash particles on the thermal radiation in biomass fired boilers

Ash is produced in combustion of biomass. Some part of this matter is called fly ash and is carried by the flow and causes not only air pollution and erosion, but also can affect the thermal radiation. The effects of fly ash particles on the thermal radiation are considered in this investigation. By analyzing sampled data in an electrostatic filter, a realistic particle size distribution is found. Although the optical data on biomass fly ash are not available, however, similarity between coal and biomass ash compositions showed that the optical constants of the low Fe coal fly ash can be applied for the biomass fly ash. The Mie theory is used to predict scattering and absorption coefficients and phase function. The mean Planck scattering and absorption coefficients and phase function are predicted by averaging over the particle size distribution and Planck function, respectively. The effects of fly ash particles on thermal radiation are evaluated by a three-dimensional test case. It is assumed that the medium is a mixture of non-grey gases and different level of particle loading. Predicted results from the test case showed that the fly ash can be influential on the thermal radiation. In addition, in selected fly ash volume fractions, the effect of scattering by particles is not so important on the radiative heat source and radiative heat flux to the wall whereas their absorption effect is important and can increase the radiative heat source and wall heat fluxes.