华能南京电厂不同粒径粉煤灰中微量元素分布及其富集规律

华能南京电厂不同粒径粉煤灰的化学成分和矿物相组成基本相同，煤粉所含矿物质在高温燃烧过程中的挥发－凝聚作用，导致微量元素趋向细粒径粒煤灰中富集，其富集的程度则与粉煤灰的平均粒径和元素的地球化学性质密切相关，粉煤灰排放的环境效应表明，尤以细粒径灰粒的影响最大。     

Leaching behavior of lignite fly ash with shake and column tests

The maximum concentration of the majority of the trace metals in the leachates from shake and column test of lignite fly ash (LFA) was within the prescribed limits; however, total dissolved solids, total hardness, cations and anions (except K⁺), being above the prescribed limits, may lead to the increase in the hardness and salinity in the soil on the disposal of LFA. Present generation of huge amount of fly ash from thermal power plants (TPPs) is a big challenge concerning contamination of soil, crop produce and surface and ground water bodies due to the presence of some of the toxic trace metals in it. The leaching behavior of alkaline LFA (pH, 10.94), from TPP of Neyveli Lignite Corporation (NLC), India, was investigated by shake and column tests using water and sodium acetate buffer. The leaching of trace metals from LFA was governed by their concentrations, association with the ash particles, leaching duration and pH of the leachate (most influencing parameter). The leaching of metals followed the order: buffer column > aqueous column > aqueous shake > buffer shake test.     

Investigating the chemical stabilization of hazardous waste material (fly ash) encapsulated in Portland cement

Portland cement has been suggested as an effective stabilization (physico-chemical) method for hazardous waste. This research explored the immobilization of metals in various mixtures of Portland cement and fly ash waste sampled from coal power plant in the province of Lodz, central Poland. The stabilization of fly ash in Portland cement was investigated under a wide range of pH conditions (3–12). Leachability tests were used to determine the efficiency of the encapsulation by studying the dissolution of alkaline metals (sodium, potassium) and alkaline earth metals (calcium, magnesium). The lowest value of leached metals was obtained for ratio of ash to cement of 1:10 in a case of sodium and calcium, while ratio 1.5 gave the lowest leached effects for potassium and magnesium. The high effectiveness of solidification/stabilization process was gained in high pH values (9–11).     

Effects of Particle Size and Chain Length on Flotation and Adsorption of Quaternary Ammonium Salts onto Kaolinite

Effects of particle size and chain length on flotation of quaternary ammonium salts (QAS) onto kaolinite have been investigated by mico-flotation tests. The two kinds of quaternary ammonium salts [RN(CH3)3] with different chain lengths, dodecyltrimethylammonium chloride (DTAC) and cetyltrimethylammonium chloride (CTAC) were used as collectors for kaolinite in different particle size fractions (0.075–0.01 mm, 0.045–0.075 mm, 0–0.045 mm). The anomalous flotation behavior of kaolinite have been further explained based on crystal structure considerations by adsorption tests and molecular dynamics (MD) simulation. The results show that the flotation recovery of kaolinite in all different particle size fractions decreases with an increase in pH when DTAC and CTAC are used as collectors. As the concentration of collectors increases, the flotation recovery increases. The longer the carbon chain of QAS is, the higher the recoveries of coarse kaolinite (0.075–0.01 mm and 0.045–0.075 mm) are. But the flotation recovery of the finest kaolinite (0–0.045 mm) decreases with chain lengths of QAS collectors increasing, which is consistent with the flotation results of unsifted kaolinite (0–0.075 mm). It is explained by the froth stability related to the residual concentration of QAS collector. In lower residual concentration, the froth stability becomes worse. Within the range of flotation collector concentration, it's easy of CTAC to be completely adsorbed by kaolinite in the particle size fraction (0–0.045 mm), which led to lower flotation recovery. Moreover, it is interesting that the particle size of kaolinite is coarser, the flotation recovery is higher. The anomalous flotation behavior of kaolinite is rationalized based on crystal structure considerations. The results of MD simulations show that the (001) kaolinite surface has the strongest interaction with DTAC, compared with the (001), (010) and (110) surfaces. On the other hand, when particle size of kaolinite is altered, the number of basal planes and edge planes is changed. It is observed that the finer kaolinite particles size become, the greater relative surface area of edges is, and the more the number of edges is. It means that fine kaolinite particles have more edges to adsorb less cationic colletors than that of coarse kaolinite particles, which is responsible for the poorer floatability of fine kaolinite.     

Coal fly ash interaction with environmental fluids: Geochemical and strontium isotope results from combined column and batch leaching experiments

The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope results from both column and batch leaching experiments show a marked increase in ⁸⁷Sr/⁸⁶Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.     

Experimental study of acidity-consuming processes in mining waste rock: some influences of mineralogy and particle size

Weathering reactions producing and consuming acid in fresh waste rock samples from the Aitik Cu mine in northern Sweden have been investigated. Batch-scale (0.15 kg) acid titrations with waste rock of different particle sizes were operated for 5 months. The pH was adjusted to a nearly constant level, similar to that in effluents from waste rock dumps at the site (pH near 3.5). The reactions were followed by analysing for all major dissolved elements (K, Na, Mg, Ca, Si, Al, SO₄, Cu, Zn, Fe) in aliquots of solution from the reaction vessels. In addition, the solids were physically and chemically characterised in terms of mineralogy, chemical composition, particle size distribution, surface area and porosity. The results show that the alkalinity production is initially dominated by a rapid dissolution of small amounts of calcite and rapidly exchangeable base cations on silicate surfaces. Steady-state dissolution of primary silicate minerals also generates alkalinity. The total alkalinity is nearly balanced by input of acid from the steady-state oxidation of sulphides, such that the pH 3.1–3.4 can be maintained without external input of acid or base. There is a large difference in weathering rates between fine materials and larger waste rock particles (diameters (d) >0.25 mm) for both sulphides and silicates. As a result particles with d smaller than 0.25 mm contribute to approximately 80% of the sulphide and silicate dissolution. Calcite dissolution can initially maintain a neutral pH but with time becomes limited by intra-particle diffusion. Calcite within particles larger than 5–10 mm reacts too slowly to neutralise the acid produced from sulphides.     

季节冻土地区路基冷阻层温度场效应

为研究季节冻土地区冷阻层的路基温度场效应,基于ANSYS软件热分析原理,以粉煤灰土、橡胶颗粒改良粉煤灰土和聚丙烯纤维改良粉煤灰土3种冷阻层材料为研究对象,模拟季节冻土地区道路路基温度场,研究其阻止热量交换的效果。结果表明：采用粉煤灰土为冷阻层的道路的最大冻深为1.32 m,温度梯度最低值为-17.606℃/m;采用橡胶颗粒改良粉煤灰土为冷阻层的道路的最大冻深为0.94 m,温度梯度最低值为-23.563℃/m;聚丙烯纤维改良粉煤灰土为冷阻层的道路的最大冻深为1.20 m,温度梯度最低值为-19.557℃/m。橡胶颗粒改良粉煤灰土冷阻效果最佳,其确保路基土处于零上温度不冻结状态的最小摊铺厚度为0.33 m,适宜作为季节冻土地区的冷阻材料。     

Leaching characteristics of fly ash

The disposal of fly ash as a byproduct of thermic power stations, results in significant environmental problems. The leaching of coal fly ash during disposal is of concern for possible contamination, especially for the aquatic environment when ash is in contact with water. The aim of this study was to investigate the leaching behaviour of fly ashes currently disposed in Kemerkoy Power Plant (Turkey) fly-ash-holding pond. The studies were conducted with fly ashes from the electrostatic precipitators (fresh fly ash) and from the fly ash pond (pre-leached fly ash). The fly ashes has alkaline in nature and pH ranges between 11.9 to 12.2. The pre-leached fly ash exhibited lower EC values (7,400 µS) than the fresh fly ash (10,300 µS). In contrast to Fe and Pb, the elements such as Cr, Cd, Cu and Co did not leach from the fly ash. The Ca and Mn concentrations decreased with increasing temperature whereas, Na and K concentrations increased. The results showed that the most important effects of fly ash leaching were pH, Na, Ca, K, Fe, Mg, Mn and Pb.     

准格尔地区粉煤灰中镓的浸出率影响因素研究

为了粉煤灰的高附加值综合利用,采用酸浸法对准格尔地区循环流化床粉煤灰进行了镓的浸出实验研究,考察了多种因素对镓的浸出率的影响,包括粉煤灰粒度,酸的种类与浓度、酸浸温度与时间、固液比等。结果表明,提高镓的浸出率的适宜条件为:粉煤灰粒度200目,盐酸的浓度6 mol/L,酸浸温度应大于160℃,酸浸时间6 h,液固比在5∶1~6∶1之间为宜。在优选的工艺条件下,镓的浸出率可达80%以上。从粉煤灰中提取镓,使其作为一种资源加以利用,是提高粉煤灰综合利用价值的有效途径。     

Temperature and pH Dependence of Some Metals Leaching from Fly Ash of Municipal Solid Waste

Abstract. Municipal solid waste combustion leads to concentration of various metals in the solid residue (fly ash) remaining after combustion. These metals pose serious environmental hazard and require proper handling and monitoring in order to control their harmful effects. Leachability of some metals from fly ash was examined in fly ash and Milli-Q water mixture (liquid-to-solid ratio, 100) under various temperature and pH conditions in the laboratory. The leaching experiments conducted for 24 hours showed that pH was generally more important than temperature in controlling the amount of metals leached out of the fly ash. However, at a given pH, rise in temperature led to different degree of (usually one to two fold) enhanced or reduced leaching of metals. Owing to amphoteric nature of oxides of Al, Cr, Pb and Zn, these metals often yielded typical pattern of increase and decrease in their concentrations with change in pH. The extent of leaching of Cr and Pb in our experiments suggests that decrease of pH to acidic range in the case of Pb and to neutral to acidic range for Cr over a long period of storage of fly ash at solid waste dumping site may facilitate leaching of these metals from fly ash, leading to contamination of groundwater to the level that exceeds beyond the level permitted by the environmental laws.     

大位移剪切下钙质砂破碎演化特性

为了揭示钙质砂在大位移剪切作用下的破碎及形状演化规律,对南海钙质砂进行了系列不同剪切位移下的环剪试验。首先,利用筛分和激光粒度分析获取试验后的颗粒粒径分布,分析颗粒分布变化情况;其次,通过粒径分布对破碎进行定量分析;最后,运用图像处理技术计算颗粒圆度和扁平度,分析了颗粒形状的变化情况。试验结果表明,在不同的竖向压力下,颗粒会达到不同的稳定级配,但达到稳定所需的剪切位移相同;经历大位移剪切后,出现粒径为0.01～0.075 mm钙质砂破碎严重的现象;随剪切位移的增加,颗粒的圆度和扁平度减小。针对细小颗粒破碎严重的现象,修正了相对破碎率;修正后的相对破碎率能考虑粒径为0.01～0.075 mm颗粒发生的破碎。剪切后的钙质砂颗粒更为规则,整体轮廓趋于圆形、表面更光滑。     

Partitioning of major and trace inorganic contaminants in fly ash acid mine drainage derived solid residues

Acid mine drainage was reacted with coal fly ash over a 24 h reaction time and species removal trends evaluated. The evolving process water chemistry was modeled by the geochemical code PHREEQC using WATEQ4 database. Mineralogical analysis of the resulting solid residues was done by X-ray diffraction analysis. Selective sequential extraction was used to evaluate the transfer of species from both acid mine drainage and fly ash to less labile mineral phases that precipitated out. The quantity of fly ash, volume of acid mine drainage in the reaction mixture and reaction time dictated whether the final solution at a given contact time will have a dominant acidic or basic character. Inorganic species removal was dependent on the pH regime generated at a specific reaction time. Sulphate concentration was controlled by precipitation of gypsum, barite, celestite and adsorption on iron-oxy-hydroxides at pH > 5.5. Increase of pH in solution with contact time caused the removal of the metal ions mainly by precipitation, co-precipitation and adsorption. PHREEQC predicted precipitation of iron, aluminium, manganese-bearing phases at pH 5.53–9.12. An amorphous fraction was observed to be the most important in retention of the major and minor species at pH > 6.32. The carbonate fraction was observed to be an important retention pathway at pH 4–5 mainly due to initial local pockets of high alkalinity on surfaces of fly ash particles. Boron was observed to have a strong retention in the carbonate fraction.     

Metal recovery from power plant ash: An ecological approach to coal utilization

The growing use of coal in electrical generation is resulting in power plant solid waste becoming a serious national problem. For 1977, approximately 62 million tonnes of utility ash was produced in the US. If oil and gas burning units that were originally designed to burn coal switch back to that fuel, utility ash will be the fourth largest solid material produced in the US. Disposing of such quantities of wastes poses siting and pollution problems which are becoming critical in areas experiencing increased land use competition.An alternative to disposal is to recover the constituent metals of the ash. Aluminium, iron, manganese, calcium, titanium, and magnesium are all present in fly ash, the utility waste that poses the major disposal problem. This paper indicates that metal recovery is an attractive alternative if national instead of special interest goals are maximized. Metal recovery from fly ash is attractive on environmental, self-sufficiency, and stragegic grounds although it may not be a wise decision for an individual entrepreneur. The geography of power plant location within the US is increasing the economical attractiveness of this potential resource since large, new facilities produce sufficient quantities of material that can be used in nearby metal smelters.     

Comparative petrophysical and geochemical characteristics of thermal and volcanic ash from southeastern India

This paper examines the difference in the geophysical and chemical characteristic of the volcanic ash and thermal fly ash to evaluate environmental pollution. Natural volcanic ash (VA) samples from Sagirelu, Cuddapah dist., Andhra Pradesh and thermal fly ash (FA) samples from the Thermal Power Station, Ennore, Chennai, were collected, analysed and compared. The particle sizes of the ash samples were determined using the laser particle size analyzer and the different surface morphological characters were studied using SEM analyses. The chemical components such as pH, major oxides, trace metals and mineral compositions were determined using pH metre, XRF and XRD methods. pH value of the volcanic ash varies from 8.5 to 8.9 indicating its alkalinity (8.5 to 9) in volcanic ash, while the thermal ash is neutral to mildly alkaline with pH varying from 6 to 7.5. Both the ash samples have higher concentration value in SiO₂ (VA - 69.25%, FA - 46%) in major oxides and Cl (VA - 0.8%, FA - 0.1%) in trace elements. Quartz is the dominant mineral in both the types of ash, however, the volcanic ash has amorphous silica, while the fly ash contains crystalline quartz.     

垃圾焚烧飞灰水泥固化体强度稳定性研究

针对垃圾焚烧飞灰安全处置技术要求,采用水泥对其进行固化、稳定化处理,研究了不同水泥添加量、不同养护时间和渗沥液浸泡时间对固化体无侧限抗压强度及破坏特性的影响,并对垃圾渗沥液的侵蚀机制进行了分析。结果表明：当水泥添加量小于5%,养护时间小于3 d时,飞灰固化体在渗沥液浸泡下迅速解体,垃圾渗沥液的侵蚀对飞灰固化体的强度有较大的影响,浸泡后的固化体呈现出明显的应变软化特征,而未经浸泡的固化体的强度增长符合y=a[1-exp(-bt)]模式。随着水泥添加量及养护时间的增加,飞灰固化体无侧限抗压强度增加,破坏应变减小,而随着浸泡时间的增加,飞灰固化体的无侧限抗压强度先增大后减小,转折点大约在5～7 d,破坏应变近似呈线性增大。渗沥液对飞灰固化体的侵蚀主要是其成分抑制了固化体水化反应和破坏了水化产物。研究成果可为垃圾焚烧飞灰的安全处置技术提供理论依据和参数支持。     

Leaching capabilities of iodine monochloride (ICl) and diethylenetriamine pentaacetic acid (DPTA) at different concentrations and pH for some major and trace metals from coal and coal fly ash

In the present study, coal from Chakwal (Pakistan) was leached with an aqueous solutions of iodine monochloride (ICl) and diethylenetriamine pentaacetic acid (DPTA) of different concentrations. The effect of stirring time, concentration and pH was studied on the leaching of different metals from coal. The physicochemical parameters indicated that the coal was of reasonably good quality. The results indicated that with increase in time duration, the extraction of metals increased. In most of the cases, metal concentration increased in the leachate with increasing the concentration of the leaching agents. DPTA was found to be the best leaching agent for most of the metals. Higher extraction of metals from coal fly ash indicated that coal organic matter has a pronounced effect on the leaching. Higher concentration of metals was extracted from virgin coal and coal fly ash at low pH (p?>?0.00) as compared to high pH. DPTA extracted metals in higher concentration from virgin coal and coal fly ash at low pH as compared to ICl. Based on the present study, the most leached metals were Fe, Cu, Mn and the least were Pb, Ni, Cd and Cr.     

Stability and leaching of cobalt smelter fly ash

The leaching behaviour of fly ash from a Co smelter situated in the Zambian Copperbelt was studied as a function of pH (5–12) using the pH-static leaching test (CEN/TS 14997). Various experimental time intervals (48 h and 168 h) were evaluated. The leaching results were combined with the ORCHESTRA modelling framework and a detailed mineralogical investigation was performed on the original FA and leached solid residues. The largest amounts of Co, Cu, Pb and Zn were leached at pH 5, generally with the lowest concentrations between pH 9 and 11 and slightly increased concentrations at pH 12. For most elements, the released concentrations were very similar after 48 h and 168 h, indicating near-equilibrium conditions in the system. Calcite, clinopyroxenes, quartz and amorphous phases predominated in the fly ash. Various metallic sulfides, alloys and the presence of Cu, Co and Zn in silicates and glass were detected using SEM/EDS and/or TEM/EDS. The leaching of metals was mainly attributed to the dissolution of metallic particles. Partial dissolution of silicate and glass fractions was assumed to significantly influence the release of Ca, Mg, Fe, K, Al and Si as well as Cu, Co and Zn. The formation of illite was suggested by the ORCHESTRA modelling to be one of the main solubility-controlling phases for major elements, whereas Co and Zn were controlled by CoO and zincite, respectively. Sorption of metals on hydrous ferric oxides was assumed to be an important attenuation mechanism, especially for the release of Pb and Cu. However, there is a high risk of Co, Cu, Pb and Zn mobility in the acidic soils around the smelter facility. Therefore, potential local options for “stabilisation” of the fly ash were evaluated on the basis of the modelling results using the PHREEQC code.     

宁东能源化工基地粉煤灰重金属赋存特征及生态风险评价

为拓展粉煤灰的资源化利用,以宁夏宁东能源化工基地鸳鸯湖电厂粉煤灰为研究对象,使用扫描电镜、能谱分析和X射线衍射等测试方法对粉煤灰理化特性进行表征和分析,并采用酸消解法、DTPA浸提法和Tessier五步提取法,对粉煤灰中铅(Pb)、铬(Cr)、镍(Ni)、铜(Cu)、镉(Cd)和砷(As)6种重金属的全量、有效态、不同形态含量进行了测定。采用风险评价编码法(RAC)、次生相与原生相比值法(RSP)和潜在生态风险指数法评估粉煤灰重金属生态风险。结果表明:(1) 粉煤灰微观结构良好,密度小,速效钾和速效磷含量丰富。(2) 粉煤灰中6种重金属元素全量和平均值均超过宁夏地区土壤环境背景值,但未超过其他农用地土壤污染风险筛选值(基本项目),超标倍数大小顺序为Pb、Cu、Cr、As、Cd、Ni。6种重金属元素有效态含量均未超过宁夏地区土壤环境背景值和其他农用地土壤污染风险筛选值。(3) RAC评价结果表明,As具有极高生态风险,Cd、Cu和Ni具有中高风险,Cr、Pb分别为低风险和无风险。RSP评价结果表明,重金属As为轻度污染,Pb、Cr、Ni、Cu、Cd均为无污染。潜在生态风险指数法结果表明,粉煤灰中6种元素全量和有效态潜在生态危害指数(RI)处于Ⅰ级,轻微生态危害水平,其中Cd是生态风险的主要贡献元素。因此,粉煤灰可以作为煤矿胶结充填材料进行大规模资源化利用。      

Characterization of activated carbon obtained from Saudi Arabian fly ash

This study investigated the potential application of heavy oil burning fly ash as a precursor to prepare activated carbon. The raw fly ash obtained from a power plant is cleaned by nitric acid/hydrochloric acid and activated at 550–800 °C with hold times of 30 and 60 min to obtain fly ash activated carbon. The phosphoric acid is used as a chemical agent to improve the surface characteristics of the cleaned fly ash. The effects of process variables such as amount of chemical reagents, activation time and temperature were investigated according to two-levels full factorial design. The resultant activated carbons were characterized in terms of Brunauer, Emmett and Teller surface area and total and pore volume. The maximum specific surface area was found of 148.30 m²/g at 800 °C temperatures with 60 min holding time. The test showed that the surface area and pore volumes of the material are also significantly enhanced by the activation process.     

Impact of co-combustion of petroleum coke and coal on fly ash quality: Case study of a Western Kentucky power plant

Petroleum coke has been used as a supplement or replacement for coal in pulverized-fuel combustion. At a 444-MW western Kentucky power station, the combustion of nearly 60% petroleum coke with moderate- to high-sulfur Illinois Basin coal produces fly ash with nearly 50% uncombusted petroleum coke and large amounts of V and Ni when compared to fly ash from strictly pulverized coal burns. Partitioning of the V and Ni, known from other studies to be concentrated in petroleum coke, was noted. However, the distribution of V and Ni does not directly correspond to the amount of uncombusted petroleum coke in the fly ash. Vanadium and Ni are preferentially associated with the finer, higher surface area fly ash fractions captured at lower flue gas temperatures. The presence of uncombusted petroleum coke in the fly ash doubles the amount of ash to be disposed, makes the fly ash unmarketable because of the high C content, and would lead to higher than typical (compared to other fly ashes in the region) concentrations of V and Ni in the fly ash even if the petroleum coke C could be beneficiated from the fly ash. Further studies of co-combustion ashes are necessary in order to understand their behavior in disposal.