准东煤燃烧中矿物质转化行为的CCSEM研究

在沉降炉中进行了准东煤的燃烧实验,利用计算机控制扫描电镜技术(computer controlled scanning electron microscopy,CCSEM)研究了煤中矿物质的转化行为。研究表明煤中主要矿物为方解石、高岭石、含铁类物质以及未分类矿物,燃烧后灰中石英、铁的氧化物、白云石的含量急剧增加,未分类矿物和方解石的含量下降。同时对3种重要致渣元素Na、Fe、Ca在燃烧前后的矿物转化行为及颗粒粒径分布进行了详细研究。     

Submicron ash formation from coal combustion

In recent years, fine particles have been found to be the cause of various harmful effects on health, and many countries have imposed restrictions on emission of these particles. Fine ash particles are formed during coal combustion in power stations and, if not collected in the air pollution control devices, are emitted into the atmosphere. The fine ash particles can remain airborne for long periods and can result in deleterious health effects when inhaled and deposited in the lungs.Previous studies have shown that combustion of coals of different rank can result in differences in the amount and chemistry of the submicron ash particles. This study examines the variability occurring between the submicron ashes formed from coals of similar rank. Five Australian bituminous coals were burned in a laminar flow drop tube furnace in two different oxygen environments to determine the amount and composition of submicron ash formed. The experimental setup is described and the repeatability of the experiments is discussed. The variability in the submicron ash yield as a percentage of the total ash collected and the submicron ash composition are presented and discussed. This paper presents experimental results rather than a detailed discussion on its interpretation. However, the results indicate that the condensation of evaporated species is responsible for the formation of ash particles smaller than 0.3 μm.     

粉煤灰高附加值利用研究进展

粉煤灰是火电厂燃煤过程中产生的固体残渣, 其成分复杂, 具有毒性, 若处理不当会对环境造成危害。因此, 粉煤灰的高附加值利用迫在眉睫。然而, 粉煤灰的品质是制约其高附加值利用的主要因素。目前, 中国粉煤灰品质参差不齐, 缺少完善的品质评价体系, 由此造成粉煤灰利用领域的局限性。针对上述问题, 首先分析了中国粉煤灰的资源化特性, 总结了粉煤灰的品质评价方法, 并重点阐述了适用于粉煤灰高附加值利用的品质评价方法;其次, 详细介绍了粉煤灰高附加值利用技术（高附加值提取技术、高附加值材料制备技术）;最后, 对粉煤灰高附加值利用的发展趋势做出了展望。     

Thermal analysis of coal ash

Carbon materials are widely used in metallurgy and in the power industry as fuels and reducing agents. Coal, although inexpensive, is difficult to use, on account of its high ash content. In the operation of industrial systems, the ash might melt, with the subsequent formation of buildup. In addition, coal ash must be stored in tailings. Therefore, fuel oil and natural gas are more commonly used. Ash tailings pose a significant environmental problem in Russia. Various methods are known for the use of ash in construction. However, their adoption has been slow, on account of the complications caused by the variability in ash composition and properties. The industrial applicability of ash may be assessed by studying the physicochemical processes that accompany ash heating and determining the relation between the properties and mineral composition of ash. An important property of ash is its fusibility, which may vary widely on account of its nonuniform mineral composition. Traditionally, the fusibility of ash is determined on the basis of State Standard GOST 32978–2014 (ISO 540:2008). As in any visual method, the results are highly inaccurate. Existing theoretical analyses employ fusibility values obtained on the basis of the international standard. In this context, there is a pressing need to develop and test new methods of determining the melting point of ash.     

合成煤中钠对煤燃烧及灰特性影响

准东煤中钠含量高，燃用时锅炉会出现严重结渣问题。通过向准东煤为原料制取的超纯煤中添加灰的模型化合物，得到合成煤。并在此基础上利用热重-差示扫描量热分析法（TG/DTG/DSC）、X射线衍射仪（XRD）和灰熔融温度测定分析手段，研究Na₂O含量对煤燃烧特性和灰熔融性的影响。结果表明：钠主要影响合成煤的着火温度（T_i）与焦炭燃烧阶段，钠含量增加使T_i升高，并且Na₂O在灰中质量分数由5%升高至8%后，钠含量增加使焦炭燃烧速率先减小后加快，并能够改善煤粉燃尽特性。钠能够降低灰熔融温度，并在Na₂O质量分数高于5%后，温度下降更加明显。在三元相图中钠对莫来石的助熔作用是造成灰熔融温度降低的重要原因。XRD分析表明Na₂O含量增加，充当骨架作用的石英在钠的助熔作用下与难熔矿物硅钙石、MgO等生成低熔点长石类矿物，这类矿物在高温下有助熔作用，能够降低灰熔融温度。同时还生成助熔性含钠矿物霞石，加剧了灰熔融。     

Study of ash deposition during coal combustion under oxyfuel conditions

This paper presents a comparative study on ash deposition of two selected coals, Russian coal and lignite, under oxyfuel (O₂/CO₂) and air combustion conditions. The comparison is based on experimental results and subsequent evaluation of the data and observed trends. Deposited as well as remaining filter ash (fine ash) samples were subjected to XRD and ICP analyses in order to study the chemical composition and mineral transformations undergone in the ash under the combustion conditions. The experimental results show higher deposition propensities under oxyfuel conditions; the possible reasons for this are investigated by analyzing the parameters affecting the ash deposition phenomena. Particle size seems to be larger for the Russian coal oxy-fired ash, leading to increased impaction on the deposition surfaces. The chemical and mineralogical compositions do not seem to differ significantly between air and oxyfuel conditions.The differences in the physical properties of the flue gas between air combustion and oxyfuel combustion, e.g. density, viscosity, molar heat capacity, lead to changes in the flow field (velocities, particle trajectory and temperature) that together with the ash particle size shift seem to play a role in the observed ash deposition phenomena.     

A mathematical model of ash formation during pulverized coal combustion

A mathematical model of ash formation during high-rank pulverized coal combustion is reported in this paper. The model is based on the computer-controlled scanning electron microscope (CCSEM) characterization of minerals in pulverized coals. From the viewpoint of the association with coal carbon matrix, individual mineral grains present in coal particles can be classified as included or excluded minerals. Included minerals refer to those discrete mineral grains that are intimately surrounded by the carbon matrix. Excluded minerals are those liberated minerals not or at least associated with coal carbon matter. Included minerals and excluded minerals are treated separately in the model. Included minerals are assumed to randomly disperse between individual coal particles based on coal and mineral particle size distributions. A mechanism of partial-coalescence of included minerals within single coal particles is related to char particulate structures formed during devolatilization. Fragmentation of excluded minerals, which is important particularly for a coal with a significant fraction of excluded minerals, is simulated using a stochastic approach of Poisson distribution. A narrow-sized sample of an Australian bituminous coal was combusted in a drop-tube furnace under operating conditions similar to that in boilers. The particle size distribution and chemical composition of experimental ash were compared to those predicted with the model. The comparisons indicated that the model generally reflected the combined effect of coalescence of included minerals and fragmentation of excluded minerals, the two important mechanisms governing ash formation for high-rank coals.     

Characterization of unburned carbon from ash after bituminous coal and lignite combustion in CFBs

This paper deals with the characterisation of carbon (UC) from bottom ash (BA) and fly ash (FA) samples from two fluidised-bed power stations burning bituminous coal and lignite. The laboratory results for the carbon determinations and its mass balances are evaluated. Chemical and mineral analyses and textural characteristics (specific surface area and pore-size distribution) are presented. Depletion/enrichment of selected elements (S, Cl, V, Cr, Ni, Cu, Zn, As, Se, Sb, Hg, and Pb) in carbon from the bottom ash are compared with both ash compostions. The strong positive relationships between the concentrations of some trace element contents (Hg, Se, As, Cu, Ni, V and Cl) in fly ash with the content of carbon and the specific surface area of FA are presented and expressed by regression equations with very high correlation coefficients. Laser ablation-ICP-MS has been used to obtain an insight into element distributions within carbon grains from the bottom ash.     

The prediction of mercury retention in ash from pulverised combustion of coal and sewage sludge

Coal-fired utility boilers and waste incinerators are the principal anthropogenic sources of atmospheric mercury. In order to provide a greater understanding of the behaviour of mercury in and downstream of a combustor, a novel mathematical model has been developed to predict mercury vaporisation and partitioning. The model has been validated in a 0.5 MW furnace, fired with pulverised coal and a coal/dried sewage sludge blend. Flue gas fly ash was sampled to ascertain the removal of mercury through fly ash adsorption and condensation at low flue gas temperatures (ca. 333 K). Mercury vaporisation, speciation, adsorbence and ash enrichment have been successfully predicted.     

Mathematical modelling of coal combustion in fluidized beds with sulphur emission control by limestone or dolomite

A model is developed for the combustion of coal in fluidized beds with sulphur emission control by limestone or dolomite. The gas and solid flow analysis is based on multiple gas bubbles of varying sizes which, accompanied by the cloud and wake, rise through the particulate emulsion phase. Solids population balance relating the feed, overflow, and elutriation with the physiocochemical changes of particles in the bed is carried out for coal and sulphur-absorbent respectively. The reactions in the bed are then formulated in terms of the above determined gas velocities and distribution functions for solids. Experimental data from various pilot-plant operations are used to assess the validity of the proposed model. The observed coal conversion and sulphur retention under various operating conditions are in good agreement with the predicted values.     

Characterisation of spouting behaviour of coal ash with thermo-mechanical analysis

Bed material agglomeration and loss of fluidization present a major problem in fluidized bed combustion or gasification of low rank coals. Ash particles start to agglomerate and fluidization becomes unstable at temperatures well below the ash softening point measured by the ASTM methods. Attempts have been made to develop a method to determine this characteristic temperature. This paper presents results from an investigation into thermo-mechanical analysis (TMA) as a potential technique. It is shown that, when applied to the coating materials at a heating rate of less than 5°C/min under a force of 0.5 N, the technique can successfully detect the point at which the particles change its spouting or fluidization characteristics.     

Fluidized bed combustion of refuse-derived fuel in presence of protective coal ash

Combustion of refuse-derived fuel (RDF) alone or together with other biomass leads to superheater fouling and corrosion in efficient power plants (with high steam values) due to vaporization and condensation of alkali chlorides. In this study, means were found to raise the portion of RDF to 40% enb without risk to boilers. This was done by co-firing RDF with coal and optimizing coal quality. Free aluminum silicate in coal captured alkalies from vaporized alkali chlorides preventing Cl condensation to superheaters. Strong fouling and corrosion were simultaneously averted. Results from 100 kW and 4 MW CFB reactors are reported.     

Fluidized bed combustion of refuse-derived fuel in presence of protective coal ash

Combustion of refuse-derived fuel (RDF) alone or together with other biomass leads to superheater fouling and corrosion in efficient power plants (with high steam values) due to vaporization and condensation of alkali chlorides. In this study, means were found to raise the portion of RDF to 40% enb without risk to boilers. This was done by co-firing RDF with coal and optimizing coal quality. Free aluminum silicate in coal captured alkalies from vaporized alkali chlorides preventing Cl condensation to superheaters. Strong fouling and corrosion were simultaneously averted. Results from 100 kW and 4 MW CFB reactors are reported.     

Study on ash deposition under oxyfuel combustion of coal/biomass blends

Combustion in an O₂/CO₂ mixture (oxyfuel) has been recognized as a promising technology for CO₂ capture as it produces a high CO₂ concentration flue gas. Furthermore, biofuels in general contribute to CO₂ reduction in comparison with fossil fuels as they are considered CO₂ neutral. Ash formation and deposition (surface fouling) behavior of coal/biomass blends under O₂/CO₂ combustion conditions is still not extensively studied. Aim of this work is the comparative study of ash formation and deposition of selected coal/biomass blends under oxyfuel and air conditions in a lab scale pulverized coal combustor (drop tube). The fuels used were Russian and South African coals and their blends with Shea meal (cocoa). A horizontal deposition probe, equipped with thermocouples and heat transfer sensors for on line data acquisition, was placed at a fixed distance from the burner in order to simulate the ash deposition on heat transfer surfaces (e.g. water or steam tubes). Furthermore, a cascade impactor (staged filter) was used to obtain size distributed ash samples including the submicron range at the reactor exit. The deposition ratio and propensity measured for the various experimental conditions were higher in all oxyfuel cases. The SEM/EDS and ICP analyses of the deposit and cascade impactor ash samples indicate K interactions with the alumina silicates and to a smaller extend with Cl, which was all released in the gas phase, in both the oxyfuel and air combustion samples. Sulfur was depleted in both the air or oxyfuel ash deposits. S and K enrichment was detected in the fine ash stages, slightly increased under air combustion conditions. Chemical equilibrium calculations were carried out to facilitate the interpretation of the measured data; the results indicate that temperature dependence and fuels/blends ash composition are the major factors affecting gaseous compounds and ash composition rather than the combustion environment, which seems to affect the fine ash (submicron) ash composition, and the ash deposition mechanisms.     

二酰异羟肟酸萃取法从粉煤灰中提取锗

利用二酰异羟肟酸 (DHYA)的磺化煤油溶液从低酸度粉煤灰浸取液中提取锗。采用相比 1 3～ 1 4 ,水相pH值为1 0 0～ 1 2 5,在室温下进行三级逆流萃取 ,使用NH4 F溶液反萃取 ,最后锗收率可达 99% ,产品纯度在 99 8%以上。     

准东煤灰熔融性与灰成分相关性分析

灰熔融性是判别结渣的主要依据之一,但部分准东煤灰熔融温度高,仍具有严重结渣倾向。为了分析准东煤灰熔融性与结渣倾向不吻合的原因,采用煤质数据对比分析法,研究了准东煤灰熔融性与煤灰成分的相关性,说明部分准东煤灰熔融性高主要是煤灰中碱性氧化物含量高引起,得出了准东煤的软化温度与煤灰中的碱性氧化物成分相关性较好,可用碱性氧化物含量/(碱性氧化物含量+酸性氧化物含量)或者当量碱性氧化物含量进行灰熔融性的初步判别,可为准东高钠煤的灰熔融性检测、锅炉设计及电厂的安全燃用提供参考和依据。     

直接燃烧法快速测定煤及煤灰中总汞含量的方法研究

探讨直接燃烧法快速测定煤及煤灰中总汞含量方法的主要性能指标,方法的精密度和正确度。结果表明,采用直接燃烧法快速测定煤及煤灰中总汞含量的方法可获得较好的准确度,其方法精密度与ASTM D6722—11中规定的精密度无显著性差异,可直接采用ASTM D6722—11中规定的精密度作为本方法的精密度。方法最佳称样量为(80±10) mg,煤灰样品最佳粒度为0.1 mm,方法检出限为0.016μg/g。     

循环流化床煤燃烧/热解多联供工艺中循环灰的密相气力输送

为考察循环流化床煤燃烧/热解多联供工艺中循环热灰的密相输送特性,在实验室建立的密相气力输送装置上分别考察了发料罐内的压力、总松动气量以及特殊位置处的松动气量等对输送固气比的影响。结果表明,在发料罐内压力一定的情况下．固气比随着总松动气量的增加而增大；发料罐内压力的增加也有利于固气比的增大；在发料罐内的压力及总松动气量一定的情况下,随着特殊位置1处松动气量的增加,固气比也随之增大。该密相气力输送方式基本可以满足CFB煤燃烧/热解多联供工艺的要求。     

Electron microscopy and phase analysis of fly ash from pressurized fluidized bed combustion

The characterization of the typical fly ashes from pressurized fluidized bed combustion system (PFBC) in Japan and Europe was carried out by electron microscopy and phase analysis using energy-dispersive X-ray spectroscopy (EDX). The purity of limestone as in-bed sulfur removal sorbent influences the desulfurization reaction. The high-purity limestone yielded both hydroxyl ellestadite and anhydrite in Japanese PFBC ashes, while dolomite-rich limestone yielded anhydrite in European PFBC ashes. When the high-purity limestone was used, hydroxyl ellestadite particles were observed as the independent particles or the rim around limestone particles. The Al₂O₃ content in the glassy phase was inversely proportional to the CaO content in the glassy phase, suggesting that the glassy phases were formed from metakaoline and calcite as end members. Since hydroxyl ellestadite, glassy phase and metakaoline are reactive under hydrothermal conditions, PFBC ashes are expected to be used as raw materials for autoclaved products.