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.     

Trace element partitioning during the firing of washed and untreated power station coals

The effect of coal washing on trace element content and combustion behaviour of four world-traded coals has been studied at rig scale. The inputs and process outputs from a 1 MW combustion test facility, including coal, bottom ash, suspended fly ash, retained ash and flue gas, have been analysed for a standard suite of 17 trace elements. The results suggest that although coal cleaning significantly reduces the total ash content of the coal, the concentrations of individual trace elements are not reduced proportionately. Combustion of the washed coals resulted in increased concentrations of trace elements in the fly ash, although total fly ash loadings were reduced. Cleaning appeared to have little effect on concentrations of gaseous trace elements in the flue gas. The partitioning of the more volatile trace elements such as mercury and selenium between the vapour and solid phase was influenced by the amount of excess oxygen in the furnace, presumably affecting carbon-in-ash levels.The results suggest that the coal cleaning undertaken for these experiments did not significantly reduce the emissions to atmosphere of trace elements. The ultimate emissions will be determined by the efficiency of the dust capture systems.     

Environmental impacts of coal combustion: A risk approach to assessment of emissions

This paper summarises some of the work performed in the Cooperative Research Centre for Coal in Sustainable Development (CCSD) on emissions from current power generation. A comprehensive approach was taken in the CCSD program to assessing environmental issues of concern for the power, and by implication the coal, industries. Here results of sampling on full scale operating plants are described, and detailed data on emission fluxes, particle size distributions, trace element concentrations as a function of particle size, and speciation of the trace elements are illustrated. The results show that particle capture in electrostatic precipitators (ESPs) is significantly less efficient than in fabric filters (FFs), particularly for submicron material, and that significant enrichment is observed in the finer particle sizes emitted from both ESPs and FFs. Results for the speciation of chromium, arsenic and selenium in coals, bottom ash and fly ash are also presented. The majority of chromium in fly ash is present in the less toxic Cr³⁺ form. Speciation of arsenic in feed coals is variable but the dominant form of As in fly ash is the less toxic As⁵⁺.     

Semi-quantitative ESCA examination of coal and coal ash surfaces

Four North American coals and their ashes were examined using the direct, surface sensitive technique of X-ray photoelectron spectroscopy (ESCA). Two US National Bureau of Standards reference coals (SRM 1632a, SRM 1635) and one ash (SRM 1633a) were used for instrument calibration. These results verified the semi-quantitative nature of ESCA and its previously determined element detection level of ≈ 10^?9 gm cm^?2 of surface (≈0.1 bulk wt%). Thus, major elements and surface concentrated trace elements were detectable for these samples. ESCA detected elements present in the coal and/or ash in different chemical environments, for example sulphur as the sulphide or sulphate and carbon as graphite, carbonyl, carboxyl or hydrocarbon. The results of this preliminary study indicate that ESCA is useful to elucidate element siting within coal; information that is difficult to determine by analytical techniques requiring sample destruction prior to analysis. Several raw coals contained fluorine and chlorine near the one per cent level. Ashing effectively concentrates the mineral fraction of a coal by an order of magnitude resulting in additional elements being detected by ESCA. The resultant detection level of elements in the original coal is thus lowered to ≈0.01 bulk wt% by ashing. It was found that fluorine and sulphur were highly concentrated on several coal ash surfaces possible indicating surface Sorption reactions during combustion. Application of ESCA in coal geochemistry and mineralogy is indicated by this study. ESCA has the potential to measure elements at the minor and possibly trace level and confirm element siting within coal and coal ash. In addition, it may be possible to identify coals from different deposits by their unique broad scan ESCA spectra fingerprints.     

Organic sulfur and hap removal from coal using hydrothermal treatment

Coal is still the major source of power for electrical generation worldwide and will continue to be in the foreseeable future. However, the inorganic elements in coal that qualify as hazardous emissions upon combustion of the coal become an increasingly important concern. Primary emphasis has been on postcombustion cleanup of these emissions, with no technology achieving overwhelming success. The precombustion technique reported here shows promise for removing trace elements as well as sulfur prior to burning the coal. This study shows that hydrothermal treatment need not be carried out at extreme conditions to effect such removal. The sulfur content and selected trace elements of some coals are reduced by 50% or more by water at conditions above the critical temperature but below the critical pressure. The study also shows that the technique was more effective on some coals than others. Results from a pilot-scale test are included in addition to bench-scale data.     

Fine particle and trace element emissions from an anthracite coal-fired power plant equipped with a bag-house in China

Fine particle and trace element emissions from energy production are associated with significant adverse human health effects. In this investigation, the fine particles and trace elements emitted from the combustion of pulverized anthracite coal at a 220 MW power plant were determined experimentally in the size range from 30 nm to 10 μm with 12 channels. The particulate size distributions and morphological characteristics before and after the bag-house were evaluated. The uncontrolled and controlled emission factors of particles are compared with the calculated values from the US Environment Protection Agency, AP-42. Size-classified relative enrichment factors of As, Hg, Se, Cd, Cr, Cu, Al, V, Zn, Mn, Fe were obtained. Relative distributions of trace elements between bottom ash, fly ash and flue gas are determined by mass balance method. The bag-house collection efficiencies of particles and trace elements in the particulate phase are obtained. Finally, the controlled and uncontrolled emission factors of elements of different particulate size fractions are obtained, which will provide useful information for PM_2.5 and PM₁₀ emission inventory development, toxic and hazardous pollutant emission estimates and emission standards established for metal-based pollutants from a pulverized coal-fired boiler.     

Mechanisms of fine particulates formation with alkali metal compounds during coal combustion

Two types of coals with different sodium (Na) and potassium (K) concentrations were burned in an electrically heated drop tube furnace, to study the formation of particulates in association to alkali metal compounds from the coals. The particulates formed from these coals during combustion were separated by a low pressure impactor (LPI). The particulates collected in each stage of the LPI were analyzed, using an atomic adsorption spectrometer (AAS). The results obtained show that ash particles have bimodal particle size distribution for both coal types. This tendency could be due to the difference of the inherent minerals in raw coals. It was further observed that Na and K were enriched in the fine particulates for both types of coal. There was a dependence of the Na enrichment on the fine particles on concentration of excluded mineral in the raw coals. This work, therefore, showed that the appearance of alkali metal in the ash particles related to the nature of Na and K concentrations in raw coals.     

Speciation of As, Cr, Se and Hg under coal fired power station conditions

Coal combustion from power stations is an important anthropogenic contributor of toxic trace elements to the environment. Some trace elements may be emitted in range of valencies, often with varying toxicity and bioavailability. Hence, determination of trace element speciation in coals and their combustion products is important for conducting comprehensive risk assessments of the emissions from coal-fired power stations. This study focuses on speciation of selected trace elements, As, Cr, and Se, in coal combustion products and Hg in flue gas, which were sampled at one Australian power station. Different analytical methods such as secondary ion mass spectrometry (SIMS), ion chromatography-inductively coupled plasma mass spectrometry (IC-ICPMS) and X-ray absorption near edge structure spectrometry (XANES) were used to determine trace element speciation in coal and ash samples. Results showed that As, Cr and Se are all present in a range of valency states in coal. Concentrations of As and Se in the bottom ash as well as the more toxic hexavalent chromium were less than the detection limits. The more toxic As³⁺ form in fly ash was at 10% of the total arsenic, while selenium was mainly found in Se⁴⁺ form. Hexavalent chromium (Cr⁶⁺) in fly ash was 2.7% of the total fly ash chromium. Mercury speciation in flue gas was determined using the Ontario Hydro sampling train and analysis technique. Approximately 58% of the total mercury in flue gas was released in the elemental form (Hg⁰), which, among all mercury species, has the highest residence time in the environment due to lower solubility. This work summarises the performance of the selected analytical techniques for speciation of trace elements.     

用于混煤燃烧控制砷排放模型研究

混煤掺烧是控制燃煤砷排放的有效方式,但由于缺乏相关的配煤模型,限制了该技术的应用。根据燃煤过程中砷的挥发释放机制,提出一种采用砷的释放指数P表征煤燃烧过程砷的释放特性的配煤模型。该模型综合考虑煤的灰分、灰中主要矿物元素含量、各矿物元素对砷的固定系数以及煤中砷含量等因素。研究结果表明,随着煤灰固定系数由23.12增至50.90,煤灰的气相砷吸附量由3.39 mg/g增至6.14 mg/g;随着释放指数P增大,砷的固定率减小,且随着温度升高,两者相关性由900℃的0.67增至1 300℃的0.86。根据P值筛选煤种进行掺烧,当掺混煤种P值差异较大时,掺烧低P值煤种不仅可降低混煤中的砷含量,还能促进高P值煤的砷在灰中富集,促进率达77.14%;掺混煤种P值差异较小时,掺烧低P值煤种会促进砷的释放。本模型可较好地筛选煤种,为混煤掺烧控制砷等痕量元素的排放提供了新的思路。     

Status of trace element emission in a coal combustion process: a review

Several important aspects are described in this paper. The occurrences of trace elements (TEs) in coal are introduced. Four main groups of trace element content level, say, >50, 10–50, 1–10 and <1 ppm, can be drawn. Trace elements partitioning in emission streams; enrichment in submicron particles; vaporization and emission in flue gas; and the mobility and leaching behavior of trace elements in coal and combustion waste are summarized. The mechanisms of trace element transformation during combustion are illustrated as following: the vaporized metals at high temperature near the combustion flame will subsequently nucleate or condense at a lower temperature downstream. These metals form a suspended aerosol along with particles. The conversion of vaporized components into various solid and/or liquid forms is the key factor influencing the final trace elements' transformation/partitioning behavior. Finally, current trace element emission control technologies are briefly introduced. To control trace elements in particle phase, electrostatic precipitators and fabric filters are mainly used. To control trace elements in vapor phase, spray dryer absorbers, wet scrubbers, condensing wet scrubbers, wet scrubbers and solid sorbent injection should mainly be used. Research needs are identified and potentially promising research topics on trace elements emission are proposed as following: (1) trace element speciation and enrichment in coal and coal ash. (2) Trace elements partitioning in combustion process. (3) Mechanisms of transformation and control technologies for easily vaporized TEs during combustion.     

Behaviour of coal mineral matter in sintering and slagging of ash during the gasification process

The mineral matter in typical feed coals used in South African gasification processes and the ash derived from gasifying such coals have been investigated using a variety of mineralogical, chemical and electron microscope techniques. The mineral matter in the feed coals consists mainly of kaolinite, with minor proportions of quartz, illite, dolomite, calcite and pyrite plus traces of rutile and phosphate minerals. The calcite and dolomite occur in veins within the vitrinite macerals, and are concentrated in the floats fraction after density separation. Some Ca and Ti also appear to be present as inorganic elements associated with the organic matter.Electron microscope studies show that the gasification ash is typically made up of partly altered fragments of non-coal rock, bonded together by a slag-like material containing anorthite and mullite crystals and iron oxide particles, with interstitial vesicular glass of calcic to iron-rich composition. Ash formation and characteristics thus appear to be controlled by reactions at the particle scale, allowing the different types of particles within the feed coal to interact with each other in a manner controlled mainly by the modes of mineral occurrence. Integration of such techniques provides an improved basis for evaluating ash-forming processes, based on quantitative phase identification, bulk and particle chemistry, and the geometric forms in which the different phases occur.     

Mineral matter and elemental concentrations in selected western canadian coals

Major and trace element analyses were performed on coals from various locations in western Canada, and on low-temperature (150 °C) and high-temperature (1000 °C) coal ash produced from these coals. Elemental analyses were carried out by X-ray fluorescence spectroscopy and intense neutron activation analyses. Based on their trace elements, the coals in this study fall into two groups: 1. low-rank coals (lignite-subbituminous) of late Cretaceous and Tertiary age; and 2. high-rank coal (bituminous-semianthracite) of Jurassic-Cretaceous age. The elemental analyses of the coals and coal ash indicate that the local conditions had considerable influence on the concentrations of certain trace elements.Antimony and selenium in coals are the only elements which are enriched relative to concentrations in the earth's crust; arsenic is concentrated in lignite to subbituminous coal, but is depleted in bituminous-anthracite coals; as expected the ash of these coals showed many more instances of enrichment.     

Fine ash formation during combustion of pulverised coal-coal property impacts

In many countries, legislation has been enacted to set guidelines for ambient concentrations and to limit the emission of fine particulates with an aerodynamic diameter less than 10 μm (PM₁₀) and less than 2.5 μm (PM_2.5). Ash particles are formed during the combustion of coal in pf boilers and fine ash particulates may potentially pass collection devices. The ash size fractions of legislative interest formed during coal combustion are the result of several ash formation mechanisms; however, the contribution of each of the mechanisms to the fine ash remains unclear. This study provides insight into the mechanisms and coal characteristics responsible for the formation of fine ash. Five well characterized Australian bituminous coals have been burned in a laminar flow drop tube furnace in two oxygen environments to determine the amount and composition of the fine ash (PM₁₀, PM_2.5 and PM₁) formed. Coal characteristics have been identified that correlate with the formation of fine ash during coal combustion. The results indicate that coal selection based on (1) char characterization and (2) ash fusion temperature could play an important role in the minimization of the fine ash formed. The implications of these findings for coal selection for use in pf-fired boilers are discussed.     

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.     

Volatility of fly ash and coal

The volatilization of fly ash has been examined by a number of techniques including TGA—DTA, Knudsen cell mass spectrometry, volatilization of neutron-activated fly ash, and X-ray fluorescence analysis of sized fly ash, low-temperature ash, and the parent coal. At low temperatures, H₂O, CO₂, SO₂, and a number of organic compounds are the primary volatile species as determined by mass spectrometry. Analysis of the volatiles collected from activated fly ash heated to temperatures up to 1400 °C shows that Hg, Se, As, Br, and I are nearly completely volatilized. The analysis of the bulk and size fractions of fly ash, and parent coal, is consistent with this and provides evidence for volatilization of 15 elements during coal combustion. Comparison of coal and fly ash compositions also shows that significant amounts of Se are still present in the gas phase at the precipitators and more than 50 wt % of the Se is contained in the stack emissions. The results are consistent with present models for fly ash formation and trace element enrichment.     

Trace elements (Mn,Cr, Pb,Se, Zn,Cd and Hg) in emissions from a pulverized coal boiler

The concentrations of seven trace elements (Mn, Cr, Pb, Se, Zn, Cd, Hg) in raw coal, bottom ash and fly ash were measured quantitatively in a 220 tons/h pulverized coal boiler. Factors affecting distribution of trace elements were investigated, including fly ash diameter, furnace temperature, oxygen concentration and trace elements' characteristics. Modified enrichment factors show more directly element enrichment in combustion products. The studied elements may be classified into three groups according to their emission features: Group 1: Hg, which is very volatile. Group 2: Pb, Zn, Cd, which are partially volatile. Group 3: Mn, which is hardly volatile. Se may be located between groups 1 and 2. Cr has properties of both Groups 1 and 3. The smaller the diameter of fly ash, the higher is the relative enrichment of trace elements (except Mn). Fly ash shows different adsorption mechanisms of trace elements and the volatilization of trace elements rises with furnace temperature. Relative enrichments of trace elements (except Mn and Cr) in fly ash are larger than that in bottom ash. Low oxygen concentration will not always improve the volatilization of trace elements. Pb forms chloride more easily than Cd during coal combustion.     

Transformation of alkali and alkaline earth metals in low rank coal during gasification

Transformation of alkali and alkaline earth metals (AAEM) in low rank coals during gasification was examined by combining computer-controlled scanning electron microscopy (CCSEM) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Two sub-bituminous coals were pyrolyzed at 1500 °C using a drop tube furnace, and the resultant chars were then gasified in CO₂ atmosphere at the same temperature. Total amounts of AAEM species in the raw coals and the chars were determined by ICP-AES. Minerals in the raw coals and ash particles in the chars were analyzed by CCSEM.AAEM species were mainly present in the raw coals as dispersed species, organically associated cations or fine mineral particles (<1 μm), which cannot be quantified by CCSEM. It was found that the dispersed Ca species were first converted into fine ash particles upon the devolatilization and then most of the particles interacted with inherent clay minerals to form complex aluminosilicates. In the case of Na and K, the dispersed species mostly vaporized and the interaction with inherent minerals was not observed.     

660MW燃煤锅炉细微颗粒物中次量与痕量元素的分布特性

应用承重撞击器(DGI)采样系统在南昌某电厂2^#锅炉电除尘器前进行颗粒物采集,并同时采集了原煤样和底灰样。对飞灰的质量粒径分布、底灰和飞灰中次量与痕量元素的分布特性进行了分析。结果表明PM_1.0和PM_2.5质量分别占PM₁₀质量的16.0%~17.4%和46.9%~50.6%;Na、Mg、P、S主要富集在亚微米颗粒物中,Al、Si、Ca、Ti、Fe、K主要富集在超微米颗粒物中;随着颗粒物粒径的减小,As、Cd、Cr、Pb的浓度逐渐增大,且在亚微米颗粒物中的增幅大于超微米颗粒物,Mn在各级颗粒物中浓度相近;As、Cd、Cr、Pb大量富集于亚微米颗粒物之上,Mn在各级颗粒物中富集特性无明显差异,且各痕量元素挥发特性存在以下规律:As>Cd>Cr>Pb>Mn;文中给出了无控制条件下痕量元素的排放因子,PM_1.0中各元素排放比例存在以下规律:As>Cd>Cr>Pb>Mn。     

Mobilisation of trace elements from as-supplied and additionally cleaned coal: Predictions for Ba, Be, Cd, Co, Mo, Nb, Sb, V and W

The partitioning of the elements antimony, barium, beryllium, cadmium, cobalt, molybdenum and vanadium between the products of combustion of coals containing them burnt as pulverised fuel in excess air has been modelled using the MTDATA thermodynamic equilibrium package with data from the MTOX silicate melt model added to the standard database and trace element data added where necessary. The coals examined were Gascoigne Wood, ElCerrejon and Harworth coals as normally supplied (washed) and after additional washing, and Binungan low ash coal only as normally supplied, represented by the analyses for coal, coal mineral and trace elements obtained in a study of the partitioning carried out in a pilot scale pf combustor by PwerGen on behalf of the United Kingdom DTI. Excess air levels were 1% for all coals and 3% in addition for Harworth. The equilibrium amount of silicate melt was predicted to fall more rapidly with falling temperature for additionally washed than for normally washed coals. It was also predicted that Ba and Co would be almost immobile, Be and V would be relatively immobile, and Sb, Cd and Mo would be mobile. Additional calculations were carried out for niobium and tungsten as trace elements in the coals, and Nb was found to be relatively immobile and W mobile. The mobilities of Ba, Be, Co, Cd, Mo, Sb and V were in agreement with those implied by the ratio of bottom ash to fly ash concentrations found in experimental investigation.     

A new rheometer for direct measurement of the flow properties of coal ash at high temperatures

Development of more effective technologies of utilising low rank coals for power generation has been driven by a demand for higher efficiency, low capital costs and minimal environmental impacts. Fluidised bed systems are regarded as one of the more promising alternative technologies for power generation to overcome the disadvantage of the existing pulverised coal burning power generation plants for low rank coals. However, ash deposition and bed agglomeration are potential problems in fluidised bed processing of coals with high alkali and sulphur contents. In order to gain a better understanding of the mechanism of agglomeration in fluidised beds, a good knowledge of the rheological behaviour of coal ash deposits at high temperatures and under the processing conditions is necessary. Rheological characterisation of materials at high temperatures is difficult due to lack of standard instruments and reliable measurement techniques. We have recently developed a rheometer that has the capability of measuring the rheological properties of coal ash slag over a wide range of temperatures from 600 to 1300°C and under different processing atmospheres. In this paper the features of this unique instrument are described and the experimental technique developed for flow property measurement is outlined. Some typical measured rheological properties of coal ashes from different Australian low-rank coals are presented and discussed to illustrate the potential applicability of the rheometer for high-temperature rheological characterisation. Furthermore, by means of the experimental results obtained it is demonstrated that the alkali content of the coal ash plays a significant role in controlling the rheological characteristics of the ash deposit, which in turn has an important implication on agglomeration in fluidised bed combustion processes.