Rheology of fly ashes from coal and biomass co-combustion

The presence of large amounts of alkali metals, chlorine and sulphur in most biomass fuels - compared to coal - can create serious ash-related problems such as deposition, agglomeration and/or corrosion. This paper discusses the viscosity characteristics of fly ash from the co-combustion of various coal/biomass blends in a pilot scale pf-boiler. The produced data provide information on the melting of the ash and its flow characteristics, as a function of temperature, which may be used to modify the temperature profile of the boiler in order to avoid slagging. Straw co-firing lowers the ash viscosity leading to higher stickiness of the ash particles. Wood co-firing has only minor effects, due to the composition of wood ash and the low percentage of wood in the coal/biomass blend.     

Biomass fly ash in concrete: Mixture proportioning and mechanical properties

ASTM C 618 prohibits use of biomass fly ashes in concrete. This document compares the properties of biomass fly ashes from cofired (herbaceous with coal), pure wood combustion and blended (pure wood fly ash blended with coal fly ash) to those of coal fly ash in concrete. The results illustrate that with 25% replacement (wt%) of cement by fly ash, the compressive strength (one day to one year) and the flexure strength (at 56th day curing) of cofired and blended biomass fly ash concrete is statistically equal to that of two coal fly ash concrete in this investigation (at 95% confidence interval). This implies that biomass fly ash with co-firing concentration within the concentration interest to commercial coal-biomass co-firing operations at power plants and blended biomass fly ash within a certain blending ratio should be considered in concrete.     

Characterisation of biomass and coal co-firing on a 3 MWth Combustion Test Facility using flame imaging and gas/ash sampling techniques

Co-firing of biomass with pulverised coal at existing coal power stations remains a practical option available to power plant operators and is being widely adopted as one of the main technologies for reducing greenhouse gas emissions. However, there is a range of technological problems that are not well understood. This paper presents experimental investigations into the co-firing of pulverised coal directly co-milled with 5–20% biomass on a 3 MWth Combustion Test Facility. A number of combustion parameters, including flame temperature and oscillation frequency and particle size distribution, were measured under a range of co-firing conditions. The gas species within the flame and fly ash in flue gas were also sampled and analysed. The experimental data collected are used to study the impact of biomass additions to pulverised coal on the combustion characteristics of the co-firing process. The relationships between the flame characteristics, gas species and ash deposition of the furnace are investigated. The results suggest that, due to the varying physical and chemical properties of the biomass fuels, the biomass additions have impact on the combustion characteristics in a very complicated way. It has been found that the biomass addition to coal would improve the combustion efficiency because of the lower CO concentrations and higher char burnout level in co-firing. In addition, NO_x emission has been found closely linked to the flame stability, and SO_x emission reduced in general for all co-firing cases.     

Coal blend combustion: fusibility ranking from mineral matter composition☆

Although coal blends are increasingly utilized at power plants, ash slagging propensity is a non-additive property of the pure coals and hence difficult to predict. Coal ash tendency to slag is related to its bulk chemistry and ash fusion temperatures, and the present study aims to compare the results obtained from thermodynamic simulation with characterization of samples obtained as outcomes of plant-based coal-blend combustion trials at three utilities located in the Centre and North of Chile. Pulverized coal and plant residues samples from five families of binary blends tested in an experimental program were characterized for chemistry, mineralogy and maceral composition. The slagging was evaluated by determination of fusion curves using the MTDATA software and NPLOX3 database for the main coal ash oxides. The ranking obtained was approximately the same as obtained from carbon in the fly ashes and from plant residues observations. The thermodynamic modeling was a valid option to predict the fusibility during the combustion of blends.     

Ash properties and environmental impact of various biomass and coal fuels and their blends

Aiming at investigating the influence of minerals in co-firing applications in existing and developing systems, as well as their environmental impact upon recycling to soils, we used a combination of techniques such as X-ray fluorescence spectroscopy, ultraviolet and visible spectroscopy, inductive coupled plasma spectroscopy, X-ray diffractometry, differential thermal analysis and fusibility analysis to characterize various biomass and coal ashes and their blends, with biomass proportions up to 20%. Slagging and fouling propensities were predicted.The results showed that biomass ashes were richer in calcium, silicon and alkali minerals and micronutrients such as Zn, Cu and Mn, in comparison to coal ashes. Some could be useful for soil amendment or the cement industry. Slagging/fouling problems should be expected in boilers operating above 1000 °C, especially those firing cotton residue, vine shoots and bituminous coal without pre-treatment. However, the environmental impact of either biomass or coal ashes upon their disposal is expected to be very low, as leaching tests have shown. For coal/biomass blends, the composition and the fusibility of the ashes varied between those of the individual components. Thus co-firing processes using the alternative fuels studied up to 20% would not entail significant limitations in the system operation or the management strategies of ashes.     

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.     

Application of chemical fractionation methods for characterisation of biofuels,waste derived fuels and CFB co-combustion fly ashes

In the important efforts to decrease the net CO₂ emissions to the atmosphere, new, alternative fuels are being included in the fuel mixes used in utility boilers. However, these fuels have ash properties that are different from those of the traditionally used fuels and in some cases technical problems, such as ash fouling and corrosion occur due to this. Therefore, diagnostic and predictive methods are developed and used to avoid such problems. Determination of the chemical association forms of important elements, such as potassium and sodium, in the fuel by chemical fractionation is a method well defined for coal and biofuels, such as wood pellets, bark and forest residues. Chemical fractionation is a step by step leaching method extracting water soluble salts in the first step, ion exchangeable elements, such as organically associated sodium, calcium and magnesium in the second step and acid soluble compounds such as carbonates and sulfates in the third step. The solid residue fraction consists of silicates, oxides, sulfides and other minerals. The compound extracted in the two first steps is considered reactive in the combustion with a few exceptions. In this work, it has been applied to some waste fuels, i.e. sewage sludge, straw and refuse derived fuel (RDF), as well as to coal and wood. The present work also includes results from combustion tests in a fluidised bed boiler where three blends of the investigated fuels were used. The fractionation results for the fuel blends are weighted results of the fractionations of the pure fuels discussed above which are compared with fractionations of their corresponding fly ashes. The co-combustion strategy gave very good results in reducing ash problems. Possible chemical mechanisms involved are discussed in the article.     

Characterisation of meat and bone mill for coal co-firing

A most interesting solution for the disposal of meat and bone meal (MBM) is co-feeding with coal in combustion plants. MBM, is however, quite different from any other traditional or alternative solid fuel in terms of chemical composition, ash content and microstructural properties. Its effects on the performance of a boiler are largely unexplored. The present paper addresses the characteristics of MBM as alternative solid fuel and the effects of co-feeding MBM (6%) and coal (94%) in a utility boiler.A first activity consisted in the characterisation of the physico-chemical properties and the reactivity of MBM. The experimental campaign included ultimate and proximate analysis, granulometric analysis, ICP, SEM, XRD. An extensive campaign of isothermal and non isothermal thermogravimetric experiments was carried out to assess the reactivity of MBM upon pyrolysis, combustion and gasification and to obtain appropriate kinetic expressions.A second activity focused on co-firing of MBM and coal. Bottom and fly ashes were collected from an industrial boiler operated with MBM and coal. Ash samples were characterised by SEM, XRD, ICP, TGA and granulometric analysis. Results of this activity showed that MBM contributes mostly to bottom ash, however also the fly ashes are different from those typically encountered when the boiler is operated with coal alone. Differences concern the chemical composition and particle size distribution of ashes, in particular a large population of very fine particles characterised by perfectly spherical shape and non negligible carbon content is observed.     

X-ray powder diffraction-based method for the determination of the glass content and mineralogy of coal (co)-combustion fly ashes

The relevance of Al-Si glass in a number of fly ash applications, such as use as a pozzolanic material, zeolite synthesis, and geopolymer production, necessitated research towards investigation of methods for an easy and consistent determination of the glass content in this coal (co)-combustion by-products. A glass standard-addition X-ray powder diffraction (XRD)-based method is proposed in this study as an alternative to the non straightforward procedure of conventional methods for determining the amorphous components, mainly by difference of the total mass and the addition of quantified crystalline species. A >99% Al-Si glass slag sample was selected as a standard for glass. A number of glass standard/fly ash mixtures were performed on Fluidized Bed Combustion (FBC) and pulverized coal combustion (PCC) fly ashes and subsequently analyzed by XRD. The method provides results closer to quantitative proportions of the Al-Si amorphous material of this (co)-combustion by-product, with a range of values <3% when compared with those obtained by the conventional Reference Intensity Method (RIM) method, demonstrating suitability and consistence of the procedure. Furthermore, by the proposed method, the requirement of previous determination of the mineral phases of conventional techniques is avoided. Coupled with the easy calculations, this allowed a fast determination of the glass content of (co)-combustion fly ash. The mineralogy of FBC and PCC fly ash was also investigated using the RIM method. The occurrence and proportions of the crystalline components in fly ash are in line with the combustion technology and their inherent operational parameters, especially the (co)-combustion temperature. The FBC fly ash shows the highest content of relic phases from feed coal (quartz, illite, calcite, and feldspars) and lower contents of amorphous components. The PCC fly ash are characterized by the highest proportions of mullite and Al-Si glass and low contents of quartz an other relict phases. The occurrence and distribution of anhydrite and Fe-oxide species appears to be related to the content of Ca and Fe in the feed fuels, showing slightly higher contents in FBC than in PCC fly ash.     

Ash transformation during co-firing coal and straw

Co-firing straw with coal in pulverized fuel boilers can cause problems related to fly ash utilization, deposit formation, corrosion and SCR catalyst deactivation due to the high contents of Cl and K in the ash. To investigate the interaction between coal and straw ash and the effect of coal quality on fly ash and deposit properties, straw was co-fired with three kinds of coal in an entrained flow reactor. The compositions of the produced ashes were compared to the available literature data to find suitable scaling parameters that can be used to predict the composition of ash from straw and coal co-firing. Reasonable agreement in fly ash compositions regarding total K and fraction of water soluble K was obtained between co-firing in an entrained flow reactor and full-scale plants. Capture of potassium and subsequent release of HCl can be achieved by sulphation with SO₂ and more importantly, by reaction with Al and Si in the fly ash. About 70–80% K in the fly ash appears as alumina silicates while the remainder K is mainly present as sulphate. Lignite/straw co-firing produces fly ash with relatively high Cl content. This is probably because of the high content of calcium and magnesium in lignite reacts with silica so it is not available for reaction with potassium chloride. Reduction of Cl and increase of S in the deposits compared to the fly ashes could be attributed to sulphation of the deposits.     

Chemical, leaching and toxicity characteristics of CFB combustion residues

Within the last years, attention has been focused on the development of clean coal technologies, based on the pulverized coal fired once-through boiler technology and the circulating fluidised bed combustion (CFBC) systems. The environmental problems provoked from those wastes due to their toxic trace element contents necessitate their detailed characterisation. Within the scope of this concept, two different coal types were used in a series of experimental trials. Fly and bottom ash samples were collected and characterised in terms of morphology, mineralogy, leaching and toxicity behaviour. According to the results, toxic trace elements are preferentially concentrated in the fly ash particles since they presented the smaller particles size. However, the chemical analysis of the ash leachates showed that are acceptable for safe disposal, since none of them exceeds the maximum EPA limits. Additionally, the Microtox toxicity test proved that fly ash leachates, which presented the higher heavy metals concentrations, caused the higher toxic effects.     

Effects of Xinjiang high calcium coal co-firing on melting characteristics of Ca-bearing minerals in ash

In this study, a high-calcium coal, a high-silicon-aluminum Xinjiang coal and their blends were burnt in a drop tube furnace. The computer-controlled scanning electron microscope (CCSEM) was used to analyze the total ash mineral composition and particle size distribution after combustion. Based on CCSEM analysis, the composition data of single particle ash was obtained. The thermodynamic equilibrium method was used to calculate the liquid phase ratio of minerals in the ash, and the effect of coal blending on the melting characteristics of calcium-containing minerals in the ash was analyzed. The results show that the organically bound Ca easily interacts with other minerals in the coal. The mineral species of Ca-bearing minerals in the bulk ash mainly depend on the included minerals in coal. Co-firing will promote the conversion of calcium-containing aluminosilicate in the ash to calcium-containing complex aluminosilicate, and at the same time promote the melting of calcium-containing minerals. Under low temperature conditions, the particle size distribution of molten calcium-containing minerals in co-fired coal ash is affected by the particle size distribution of the alkali metal; however, under high temperature conditions, co-firing promotes the migration of molten calcium-containing minerals to large particle size ash.     

Leaching characteristics of selected Korean fly ashes and its implications for the groundwater composition near the ash disposal mound

Currently only 20% of the fly ash produced in Korea is utilised for industry, and the remainder is disposed as waste in landfill sites. Both anthracite and sub-bituminous coals are burnt in Korea. Fly ash and coal samples were collected from five different coal-fired power stations in Korea and analysed for their chemistry and mineralogy. Batch leaching tests were also carried out to investigate the leaching behaviour of selected fly ashes. The fly ash leachate chemistry was compared with the groundwater taken directly from the monitoring well installed in one of the power stations. The anthracite coals contain illite, pyrophyllite and kaolinite whereas kaolinite is the representative clay mineral for the sub-bituminous coals. Anthracite coals were higher in Si, Al and K than the sub-bituminous coals, reflecting higher mineral matter contents in the anthracite coals. Mullite and quartz are the main mineral phases for two different types of the fly ashes, with some iron oxides. The chemical compositions of the anthracite and sub-bituminous fly ashes are comparable with each other, except for extraordinary high concentrations of Cr for one anthracite fly ash. Most of the trace elements in the ash were enriched in the finer fraction, indicating surface associations. Although, some elements including Na, K, Ca and Cu were released rapidly in the initial stage of leaching, measurable amounts of metals were still detectable in the fly ash leachate treated several times with distilled water. Such leaching behaviour indicates slow and long-term leaching of elements associated with the glass fractions of the ash particle. This was confirmed by leaching of weathered fly ash, which had been disposed of for several years. Comparison of the ash leachate, treated with 0.1N-HCl, fly ash slurry in the ash pond and the groundwater indicate the influence of the ash leachate from the ash disposal mound on the groundwater composition.     

新疆高钙煤混烧对灰中含钙矿物熔融特性影响

选用一种高钙和一种高硅铝新疆煤,在沉降炉中进行不同比例的混煤和单煤燃烧实验。采用计算机控制扫描电镜（CCSEM）分别对燃烧后总灰矿物成分和粒径分布进行分析。基于CCSEM分析获取单颗粒灰成分数据,采用热力学平衡方法对灰中矿物液相比例进行计算,分析混煤燃烧对灰中含钙矿物熔融特性影响。结果表明,煤中有机结合态Ca极易与煤中其他矿物元素发生交互反应,交互反应后含钙矿物种类取决于煤中内在矿种类。混煤燃烧会促进灰中含钙硅铝酸盐向含钙复杂硅铝酸盐转化,同时促进含钙矿物的熔融。在低温条件下,混烧煤灰中熔融含钙矿物粒径分布受碱金属粒径分布影响;但是高温条件下,混烧促进熔融含钙矿物向大粒径煤灰迁移。     

Heavy metal characterization of CFB-derived coal fly ash

The present study investigates the heavy metal content of coal fly ash (FA) samples coming from three different sampling points (secondary cyclone, cooler and filter) of a pilot plant combustion facility. The combustion experiments were carried out in a 0.1 MW Circulated Fluidized Bed (CFB) boiler using South African coal, with the addition of limestone for sulfur capture. FA was tested for the presence of selected heavy metals using inductively coupled plasma optical emission spectrometry (ICP-OES); batch leaching tests were conducted as well. The samples were also characterized in terms of their microstructure, chemical and mineralogical composition, total surface area and particle size distribution. Most of the studied metals (Cd, Cr, Cu, Ni, Mn, Zn) showed enrichment in the fine, filter FA particles, while Pb was mostly concentrated in the cooler sample. Regarding leaching characteristics of the examined samples, Cr was found to occur in considerable amounts. Although the use of CFB technology for the combustion of solid fuels steadily gets bigger worldwide, only a very limited number of studies have environmentally assessed CFB-coal FAs to date. Thus, the current study aims to contribute toward building a more integrated knowledge on the environmental impact of this abundant power production by-product.     

利用差示扫描量热法测定CFBC脱硫灰中残留碳的研究

借助差示扫描量热分析仪对煤与高硫石油焦混烧排放的CFBC(循环流化床)脱硫灰的残留碳含量进行了测定,研究表明:(1)CFBC脱硫灰的热反应过程主要分为水分和挥发分逸出,碳氧化和矿物分解及继续反应等三个阶段.(2)是否含有氢氧钙石对CFBC脱硫灰的热反应过程影响很大,含有氢氧钙石的CFBC脱硫灰在碳氧化和矿物分解阶段(约...     

Utilization of fly ash coming from a CFBC boiler co-firing coal and petroleum coke in Portland cement

Fly ash coming from a circulating fluidized bed combustion (CFBC) boiler co-firing coal and petroleum coke (CFBC fly ash) is very different from coal ash from traditional pulverized fuel firing due to many differences in their combustion processes, and thus they have different effects on the properties of Portland cement. The influences of CFBC fly ash on the strength, setting time, volume stability, water requirement for normal consistency, and hydration products of Portland cement were investigated. The results showed that CFBC fly ash had a little effect on the strength of the Portland cement when its content was below 20%, but the strength decreased significantly if the ash content was over 20%. The water requirement for normal consistency of cement increased from 1.8% to 3.2% (absolute increment value) with an addition of 10% CFBC fly ash; and the free lime (f-CaO) content of CFBC fly ash affected the value of increasing. The setting time decreased with an increase of CFBC fly ash content. The volume stability of the cement was qualified even when the content of SO₃ and f-CaO reached 4.48% and 3.0% in cement, respectively. The main hydration productions of cement with CFBC fly ash were C-S-H (hydrated calcium silicate), AFt (ettringite), and portlandite.     

Co-combustion of pulverized coal and solid recovered fuel in an entrained flow reactor - General combustion and ash behaviour

Co-combustion of a bituminous coal and a solid recovered fuel (SRF) was carried out in an entrained flow reactor, and the influence of additives such as NaCl, PVC, ammonium sulphate, and kaolinite on co-combustion was investigated. The co-combustion experiments were carried out with SRF shares of 7.9 wt.%, 14.8 wt.% and 25 wt.%, respectively. The effect of additives was evaluated by maintaining the share of secondary fuel (mixture of SRF and additive) at 14.8 wt.%. The experimental results showed that the fuel burnout, NO and SO₂ emission in co-combustion of coal and SRF were decreased with increasing share of SRF. The majority of the additives inhibited the burnout, except for NaCl which seemed to have a promoting effect. The impact of additives on NO emission was mostly insignificant, except for ammonium sulphate which greatly reduced the NO emission. For SO₂ emission, it was found that all of the additives increased the S-retention in ash. Analysis of the bulk composition of fly ash from different experiments indicated that the majority of S and Cl in the fuels were released to gas phase during combustion, whereas the K and Na in the fuels were mainly retained in ash. When co-firing coal and SRF, approximately 99 wt.% of the K and Na in fly ash was present in water insoluble form such as aluminosilicates or silicates. The addition of NaCl, PVC, and ammonium sulphate generally promoted the vaporization of Na and K, resulting in an increased formation of water soluble alkalis such as alkali chlorides or sulphates. The vaporization degree of Na and K was found to be correlated during the experiments, suggesting an interaction between the vaporization of Na and K during pulverized fuel combustion. By collecting deposits on an air-cooled probe during the experiments, it was found that the ash deposition propensity in co-combustion was decreased with increasing share of SRF. The addition of NaCl and PVC significantly increased the ash deposition propensity, whereas the addition of ammonium sulphate or kaolinite showed a slight reducing effect. The chlorine content in the deposits generally implied a low corrosion potential during co-combustion of coal and SRF, except for the experiments with NaCl or PVC addition.     

The fate of trace elements and bulk minerals in pulverized coal combustion in a power station

The behaviour of 15 trace elements (As, Ba, Cr, Cu, Mn, Mo, Nb, Ni, Pb, Rb, Sr, V, Y, Zn and Zr) and 10 major and minor elements (Al, Ca, Fe, K, Mg, Na, P, S, Si and Ti) in coal during combustion in a power station has been studied. Synchronized sampling of pulverized coal, bottom ash and fly ash was undertaken over a limited time period. Fly ash morphology was studied by SEM and the mineral composition was studied by EDX and XRD. Major, minor and trace elements were determined by XRF and AAS. Differences between the composition of the ashes of pulverized coal, bottom ashes and fly ashes have been observed. As, Cu, Mo, Pb and Zn were concentrated in the fly ash. The relationship between the composition of the fly ashes and their particle size was studied. Enrichment factors were calculated for each element in different size fractions. As the particle sizes of fly ash decrease, the concentrations of As, Cu, Mo, Pb and Zn increase. From the different composition of bottom ashes and fly ashes (and relying on the results of the characterization of the feed coal carried out in previous work), it can be assumed that pyrite and carbonates make a greater contribution to the furnace bottom ashes. Quartz carries through into the fly ash. This mineral is almost absent in the finest fractions, reflecting the absence of small quartz particles in the feed coal.     

焦化除尘灰的燃烧性研究

为了扩大高炉喷吹用煤煤源,降低高炉喷吹用煤成本,本试验探索用廉价的焦化除尘灰代替部分无烟煤用于高炉喷吹的可行性。采用热重分析法对混合煤粉燃烧性进行了研究,考察了其着火温度、最大燃烧失重速率和燃尽温度等燃烧特征参数。计算了混合煤粉的综合燃烧特性指数,进而评价各混合煤粉的综合燃烧性能。初步研究表明：高炉喷吹用煤中配入适当比例的焦化除尘灰,对高炉喷吹用煤的反应性影响不大。在焦化除尘灰的配比小于5%的条件下用作高炉喷吹是可行的。