An examination of the exothermic nature of fluidized bed combustion (FBC) residues

Circulating fluidized bed combustion (CFBC) ashes from nine operational periods at the 183 MWe CFBC boiler at Point Aconi were examined for exothermic behaviour. Bed ashes and fly ashes were investigated using a Parr 1455 solution calorimeter. Limited tests were also carried out with additional samples from Point Aconi and from the 160 MWe TVA Bubbling Fluidized Bed Combustion boiler to evaluate the effects of particle size and aging on exothermic behaviour. For the Point Aconi ashes, heat release from the bed ash ranged from 11 to 52 J/g, and the maximum heat release rates ranged from 0.06 to 0.17 J/g/s. For the fly ash heat release varied from 114 to 187 J/g and the maximum heat release rates ranged from 0.8 to 1.9 J/g/s. In the fly ash samples, 50% or more of available CaO was converted to Ca(OH)₂, while for the bed ash a third or less of the CaO was converted to Ca(OH)₂. The exothermicity of the bed ash is directly proportional to the CaO content of the ash. However, this is not true for the fly ash. The exothermic behaviour of fresh FBC ash appeared to be greatly reduced by exposure in air over a 48-h period. Another conclusion of this work is that particle size effects the exothermic behaviour.     

Advanced ash management technologies for CFBC ash

The combustion of high-sulphur coal demands the reduction of sulphur emissions. The sorbent most often used in sulphur capture technology is calcium-based. Ashes from technologies such as circulating fluidized bed combustion (CFBC), therefore, contain high calcium levels. The use and disposal of these ashes poses challenges, because of highly exothermic reactions with water, high-pH leachates, and excessive expansion of solidified materials. This paper looks at the potential of two post-combustion ash treatment processes, CERCHAR hydration and AWDS disposal, in solving these challenges. A high-sulphur coal-derived CFBC ash is examined, after CERCHAR hydration treatment, in conjunction with a conventionally hydrated ash, in a range of chemical, geotechnical and utilization scenarios. The ashes are used to make no-cement and roller-compacted concrete as well as Ash Water Dense Suspensions (AWDS). The solidified mortar paste from no-cement concrete is subjected to an extensive geochemical examination to determine how solidification progresses and strength develops, from a chemical point of view.     

沸腾炉大气污染物的生成与排放特征分析

以20台沸腾炉(功率小于等于60 MW)的燃料特性分析数据和大气污染物的排放实测数据为基础,利用统计分析方法,研究了燃烧过程中排放的颗粒物(PM)、SO_2和NO_x初始排放浓度的影响因素,分析了沸腾炉PM、SO_2和NO_x排放现状,探讨了我国中小型沸腾炉PM、SO_2和NO_x排放管理控制的潜力和可行性.实验结果表明:在锅炉运行负荷大于等于80%的条件下,中小型沸腾炉PM的初始排放浓度基本上不受锅炉出力、过量空气系数和燃煤灰分含量的影响;燃煤的硫含量越高,SO_2初始排放浓度越高;过量空气系数越大,燃煤挥发分越低,NO_x初始排放浓度越高.     

固硫灰固化焦化废水处理外排污泥

采用机械力化学法活化循环流化床燃煤固硫灰,用于固化焦化废水处理外排污泥(CWT污泥)。探讨了固硫灰活化条件,并通过XRD和FTIR分析了固硫灰固化CWT污泥中重金属的机理。实验结果表明:当m(Ca O)∶m(Ca O+固硫灰)为20%、球磨频率为40 Hz、球磨时间为2 h时,养护28 d固硫灰固化体的平均抗压强度达到72.2 MPa;当污泥掺加量为50%(w)时,养护28 d含污泥固化体的抗压强度达到8.5 MPa,固化体浸出液中Pb2+和As5+的质量浓度分别为0.177 mg/L和0.013 mg/L,均远低于GB 5085.3—2007《危险废物鉴别标准浸出毒性鉴别》的规定限值。XRD和FTIR表征结果表明,在固硫灰活化过程中,混合体系水化生成了C—S—H凝胶、斜方钙沸石和钙矾石,可通过物理包裹、吸附及离子交换的形式实现CWT污泥中Pb2+和As5+的固化/稳定化。     

The long term behaviour of CFBC ash-water systems

Circulating fluidized bed combustion (CFBC) ashes in contact with water, whether in liquid or vapour form, exhibit considerable chemical activity, which can continue for more than a year. From the point of view of the setting of CFBC ash-water mixtures and their behaviour, the formation of gypsum and of ettringite are important. The crystallisation of ettringite is associated with expansion of the set mass and absorption of water into the solids, but the ash-water system as a whole shrinks. The extent of ettringite formation is reduced if carbonation of free lime can take place. There is little carbonation if the set solids are covered by water but if contact with air is not restricted, the ettringite formed earlier slowly decomposes, its place being taken by calcite and gypsum. The fate of the aluminium from decomposed ettringite is uncertain; no new crystalline Al compounds are found. It appears that ultimately most analytical lime present can become carbonated. This is environmentally beneficial since it reduces chemical activity in the landfill, and reduces the amount of CO2 released due to limestone use. The main features of the behaviour of CFBC ash-water mixtures can be reproduced in model systems (CaO-Al2O3-CaSO4-H2O) but that of real ashes is complicated by the presence of silicates and possible interactions between silica and the strongly alkaline aqueous medium. Also, aluminates present in the ash are probably more active with respect to ettringite formation than pure aluminum hydroxide.     

LIFAC ash--strategies for management

LIFAC is a more recent addition to flue gas desulphurization methods for reducing sulphur emissions during coal combustion for the production of electricity. Ashes from the combustion of a low-sulphur lignite coal using LIFAC technology were used to evaluate different ash management strategies. The ashes, as produced and after treatment by the CERCHAR hydration process, were examined for their disposal characteristics and their utilization potential in concrete. They were also evaluated as underground disposal material using the AWDS process.     

Legislative and environmental issues on the use of ash from coal and municipal sewage sludge co-firing as construction material

For the economy of any co-firing process, it is important that the common waste management options of ash remain practical. Ash from bituminous coal combustion is typically handed to the construction industry. This paper describes the current European legislation on use of ash for construction purposes. Also, it presents an experimental study on the suitability of fly ash from combustion of mixtures of bituminous coal and municipal sewage sludge as additive to cement and concrete, and for use in open-air construction works, based on the ash chemical composition and the characteristics of the extract of the ash. Presently, two European standards forbid the use of ash from co-firing as additive to cement or concrete. This study shows that ash derived from coal and sewage sludge co-firing contains generally less unburned carbon, alkali, magnesium oxide, chlorine, and sulfate than coal ash. Only the concentration of free lime in mixed ash is higher than in coal, even though, at least up to 25% of the thermal input, still below the requirements of the standards. This ash also meets the requirements for the use of fly ash in open-air construction works--concentration and mobility of few elements--although this management option is forbidden to ash from co-firing. The leaching of Cd, Cr, Cu, Ni, Pb and Zn was investigated with three leaching tests. The concentration of these metals in the extracts was below the detection limit in most cases. The concentration of Cu and Zn in the extract from fly ash was found to increase with increasing share of sewage sludge in the fuel mixture. However, the concentration of these two metals in the extract is not regulated. This study indicates that excluding a priori the use of ash from co-firing as a suitable additive for construction material could cause an unnecessary burden on the environment, since probably ash would have to be disposed of in landfill. However, allowing this requires the modification of current European standards to include limitations on all elements and compounds, absent in coal but which might be present in other fuels, that are deleterious for the quality of construction materials.     

Gypsum treated fly ash as a liner for waste disposal facilities

Fly ash has potential application in the construction of base liners for waste containment facilities. While most of the fly ashes improve in the strength with curing, the ranges of permeabilities they attain may often not meet the basic requirement of a liner material. An attempt has been made in the present context to reduce the hydraulic conductivity by adding lime content up to 10% to two selected samples of class F fly ashes. The use of gypsum, which is known to accelerate the unconfined compressive strength by increasing the lime reactivity, has been investigated in further improving the hydraulic conductivity. Hydraulic conductivities of the compacted specimens have been determined in the laboratory using the falling head method. It has been observed that the addition of gypsum reduces the hydraulic conductivity of the lime treated fly ashes. The reduction in the hydraulic conductivity of the samples containing gypsum is significantly more for samples with high amounts of lime contents (as high as 1000 times) than those fly ashes with lower amounts of lime. However there is a relatively more increase in the strengths of the samples with the inclusion of gypsum to the fly ashes at lower lime contents. This is due to the fact that excess lime added to fly ash is not effectively converted into pozzolanic compounds. Even the presence of gypsum is observed not to activate these reactions with excess lime. On the other hand the higher amount of lime in the presence of sulphate is observed to produce more cementitious compounds which block the pores in the fly ash. The consequent reduction in the hydraulic conductivity of fly ash would be beneficial in reducing the leachability of trace elements present in the fly ash when used as a base liner.     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

煤粉锅炉飞灰份额影响因素分析

通过对10个电厂22台机组36组实测数据的分析,论述了燃煤挥发分、灰分及过剩空气系数对煤粉锅炉飞灰份额的影响趋势。     

Mercury Capture on Fly Ash and Sorbents: The Effects of Coal Properties and Combustion Conditions

The US fleet of coal-fired power plants, with generating capacity of just over 300 GW, is known to be a major source of domestic mercury (Hg) emissions. To address this, in March 2005, the Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR) to reduce emissions of mercury from these plants. It is generally believed that most of the initial (Phase I) mercury reductions will come as a co-benefit of existing controls used to remove particulate matter (PM), SO₂, and NO _X . Deeper reductions in emissions (as required in Phase II of CAMR) may require the installation of mercury-specific control technology. Duct injection of activated carbon sorbents is the mercury-specific control technology that has been most widely studied and has been demonstrated over a wide range of coal types and combustion conditions. The effectiveness of the mercury control options (both “co-benefit control” and “mercury-specific control”) is significantly impacted by site-specific characteristics such as the combustion conditions, the configuration of existing air pollution controls, and the type of coal burned. This paper identifies the role of coal properties and combustion conditions in the capture of mercury by fly ash and injected sorbents.     

Reuse potential of low-calcium bottom ash as aggregate through pelletization

Coal combustion residues which include fly ash, bottom ash and boiler slag is one of the major pollutants as these residues require large land area for their disposal. Among these residues, utilization of bottom ash in the construction industry is very low. This paper explains the use of bottom ash through pelletization. Raw bottom ash could not be pelletized as such due to its coarseness. Though pulverized bottom ash could be pelletized, the pelletization efficiency was low, and the aggregates were too weak to withstand the handling stresses. To improve the pelletization efficiency, different clay and cementitious binders were used with bottom ash. The influence of different factors and their interaction effects were studied on the duration of pelletization process and the pelletization efficiency through fractional factorial design. Addition of binders facilitated conversion of low-calcium bottom ash into aggregates. To achieve maximum pelletization efficiency, the binder content and moisture requirements vary with type of binder. Addition of Ca(OH)₂ improved the (i) pelletization efficiency, (ii) reduced the duration of pelletization process from an average of 14–7 min, and (iii) reduced the binder dosage for a given pelletization efficiency. For aggregate with clay binders and cementitious binder, Ca(OH)₂ and binder dosage have significant effect in reducing the duration of pelletization process.     

在线飞灰测碳仪在燃煤锅炉中的应用

介绍了在线飞灰测碳仪工作原理和系统结构,通过其在中石化某自备电厂燃煤锅炉的实际应用,说明了燃煤锅炉使用在线飞灰测碳仪后,锅炉司炉能随时掌握飞灰含碳量波动情况,及时调整风粉比,合理控制飞灰含碳量指标,从而降低了发电成本,提高了机组运行的经济性。     

Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine

This paper presents the study of the combustion of char residues produced during co-gasification of coal with pine with the aim of characterizing them for their potential use for energy. These residues are generally rich in carbon with the presence of other elements, with particular concern for heavy metals and pollutant precursors, depending on the original fuel used.The evaluation of environmental toxicity of the char residues was performed through application of different leaching tests (EN12457-2, US EPA-1311 TCLP and EA NEN 7371:2004). The results showed that the residues present quite low toxicity for some of pollutants. However, depending on the fuel used, possible presence of other pollutants may bring environmental risks.The utilization of these char residues for energy was in this study evaluated, by burning them as a first step pre-treatment prior to landfilling. The thermo-gravimetric analysis and ash fusibility studies revealed an adequate thermochemical behavior, without presenting any major operational risks.Fluidized bed combustion was applied to char residues. Above 700 °C, very high carbon conversion ratios were obtained and it seemed that the thermal oxidation of char residues was easier than that of the coals. It was found that the char tendency for releasing SO₂ during its oxidation was lower than for the parent coal, while for NO_X emissions, the trend was observed to increase NO_X formation. However, for both pollutants the same control techniques might be applied during char combustion, as for coal. Furthermore, the leachability of ashes resulting from the combustion of char residues appeared to be lower than those produced from direct coal combustion.     

Utilization of blended fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash in geopolymer

In this paper, synthesis of geopolymer from fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash was studied in order to effectively utilize both ashes. FBC-fly ash and bottom ash were inter-ground to three different finenesses. The ashes were mixed with as-received PCC-fly ash in various proportions and used as source material for synthesis of geopolymer. Sodium silicate (Na₂SiO₃) and 10 M sodium hydroxide (NaOH) solutions at mass ratio of Na₂SiO₃/NaOH of 1.5 and curing temperature of 65 °C for 48 h were used for making geopolymer. X-ray diffraction (XRD), scanning electron microscopy (SEM), degree of reaction, and thermal gravimetric analysis (TGA) were performed on the geopolymer pastes. Compressive strength was also tested on geopolymer mortars. The results show that high strength geopolymer mortars of 35.0–44.0 MPa can be produced using mixture of ground FBC ash and as-received PCC-fly ash. Fine FBC ash is more reactive and results in higher degree of reaction and higher strength geopolymer as compared to the use of coarser FBC ash. Grinding increases reactivity of ash by means of increasing surface area and the amount of reactive phase of the ash. In addition, the packing effect due to fine particles also contributed to increase in strength of geopolymers.     

煤燃烧过程中金属元素迁移特性

利用ICP-AES光谱仪对原煤、飞灰和底灰中铝、钾、钙、镁、铁、锰、锌、铜、硒、铬、砷等11种元素的含量进行了分析;对上述元素在煤燃烧过程中的迁移挥发特性进行了讨论,结果是钙、锰、铁挥发性较小,主要沉积在底灰中,而锌、铜挥发性较大,其他元素属于中等挥发性。     

Influence of flue-gas desulfurization systems on coal combustion by-product quality at kentucky power stations burning high-sulfur coal

Two Kentucky power plants burning similar blends of high-sulfur western Kentucky and southern Indiana coal provide a unique opportunity to examine the variations in coal combustion by-products due to differences in the method of wet flue-gas desulfurization (FGD). One plant employed carbide lime-based scrubbing for two units and a dual-alkali process for the third unit. The second plant employed a Mississippian limestone from Kentucky for all four units. This study provides an example of optical and SEM petrographic techniques, supplemented by chemical analyses, applied to the study of, at least from the geologic perspective, non-traditional materials. The coal sources comprise a blend of high volatile C and B bituminous, high vitrinite (85–90%, mmf), high-sulfur (> 3%, dry) coals. The fly ash is dominated by glassy phases (70–80%) with about 5–10% spinel (predominately magnetite), 3–10% quartz, and 4–10% isotropic coke comprising the remaining portion of the ash. SEM observations indicate that the glassy particles exhibit a bimodal size distribution with sub-micron glass spheres and a population of larger (several 10s of microns) spheres. The bottom ash has higher proportions of spinels and mullite, with negligible carbon forms, compared to the fly ash from the same units. Fly ashes were observed to be lower in Fe and higher in Al, Si, and S compared to the bottom ashes. Carbide lime, a by-product of acetylene manufacture, soda ash, and limestone were the reagents used in the flue-gas desulfurization processes. The primary FGD by-product is a calcium sulfite slurry which is vacuum filtered and mixed with fly ash and, usually, lime, to form a stable product for disposal. The FGD by-products have some potential, as yet unrealized, for utilization.     

Role of aluminous component of fly ash on the durability of Portland cement-fly ash pastes in marine environment

The durability, of mixtures of two kinds of Spanish fly ashes from coal combustion (ASTM class F) with 0, 15 and 35% replacement of Portland cement by fly ash, in a simulated marine environment (Na(2)SO(4)+NaCl solution of equivalent concentration to that of sea water: 0.03 and 0.45 M for sulphate and chloride, respectively), has been studied for a period of 90 days. The resistance of the different mixtures to the attack was evaluated by means of the Koch-Steinegger test. The results showed that all the mixtures were resistant, in spite of the great amount of Al(2)O(3) content of the fly ash. The diffusion of SO(4)(2-), Na+ and Cl- ions through the pore solution activated the pozzolanic reactivity of the fly ashes causing the corresponding microstructure changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Biobased Contents of Organic Fillers and Polycaprolactone Composites with Cellulose Fillers Measured by Accelerator Mass Spectrometry Based on ASTM D6866

The biobased contents of raw materials such as starches, sugar, chitin, or wood powders for biomass plastics were measured using Accelerator Mass Spectrometry (AMS) based on ASTM D6866. AMS measures the isotope carbon ratio of ¹⁴C to ¹²C and ¹³C in graphite derived from sample powders. The biobased contents of starches, sugar or chitin were almost 100% which means that they are fully biobased. The biobased contents of the wood powders were over 140% due to the effect of the post 1950s ¹⁴C injection due to nuclear testing. Poly(ε-caprolactone) (PCL) composite samples were prepared using the polymerization and direct molding method. The starting compound was the ε-caprolactone monomer liquid combined with cellulose and inorganic fillers using aluminum triflate as a catalyst at 80 °C for 6 or 24 h. PCL cylinder-shaped composite samples with a homogeneously dispersed cellulose filler were prepared with M_n = 4,600 (M_w/M_n = 2.9). The biobased content of the PCL composite with 50 wt% cellulose filler (51.67%) measured using AMS was slightly higher than the carbon ratio of cellulose in the starting powder samples (41.3 mol%). This is due to the higher biobased content (112.70%) of the cellulose filler used in this study. The biobased content of the polymer composite powders by AMS was found not to be affected by the presence of inorganic fillers, such as talc.     

An investigation on pollutant emissions from co-firing of RDF and coal

Pollutant emissions from co-firing of refuse derived fuel (RDF) and coal were investigated in a vortexing fluidized bed combustor (VFBC). RDF-5 was made of common municipal solid waste (MSW). CaCO₃ was injected in the combustor to absorb HCl at 850 °C. The results show that NO_x and HCl emissions increase with RDF-5 co-firing ratio. The NO_x concentration in flue gas at the bottom of the combustor is higher than that at the top. However, the trend of HCl released is reverse compared with NO_x emissions. It was found that the HCl concentration decreases with increasing the molar ratio of Ca/Cl. However, the effect of CaCO₃ addition on HCl retention is not significant when the molar ratio of Ca/Cl is higher than 5. The chlorine content in fly ash increases obviously with the molar ratio of Ca/Cl. PCDD/Fs emissions decrease slightly with an addition of CaCO₃. In this study incomplete combustion is regarded as the main cause for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation.