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.     

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。     

利用提钾废渣和粉煤灰制备矿物聚合材料的实验研究

利用富钾岩石提钾后的废渣代替硅酸钠 (钾 )、大部分高岭石和氢氧化钠 (钾 ) ,以粉煤灰为主要原料 ,制备出矿物聚合材料 ,并采用正交实验确定其优化工艺条件为 :煅烧高岭石用量为 10 %～ 15 % ,废渣用量约 35 % ,氢氧化钠用量为 5 %～ 6 %。代表性样品的 7d抗压强度可达到 4 0～ 5 0MPa ,耐酸性、耐碱性分别为 99.99%和 10 0 % ,密度1.77～ 1.88g/cm3 ,收缩率 0 .13%～ 0 .2 8% ,导热系数 0 .4 8～ 0 .5 1W/m·K ,平均硬度 3.4 3。X射线粉末衍射分析表明 ,由铝硅酸盐聚合反应形成的基体相呈非晶态。扫描电镜分析絮凝状的基体相与粉煤灰玻璃体结合紧密 ,从而为制品具备良好的力学性能提供了结构基础。该矿物聚合材料成本低廉 ,同时又能利用粉煤灰等工业固体废物而达到改善环境的目的     

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.     

粉煤灰和二灰对桂林红黏土力学性质的影响

为了研究粉煤灰和二灰掺量及养护时间对桂林红黏土的改良效果,进行了直剪试验、固结试验以及电镜扫描试验。试验结果表明,粉煤灰的掺入提高了红黏土的抗剪强度,但超过一定量（18%粉煤灰掺量）反而会降低红黏土黏聚力,各掺量粉煤灰红黏土随养护龄期的延长,抗剪强度呈先增后缓趋势。二灰改良红黏土,在早期强度剧增,且强度随养护时间增长而大幅增加,一定龄期内,二灰红黏土黏聚力随二灰掺量呈先增后减趋势。粉煤灰和二灰的掺入均增大了红黏土的压缩模量,且随养护时间的延长而逐渐增大。红黏土中随粉煤灰、石灰的加入,发生一系列物理化学反应,从微观结构分析得知土中孔隙减少,结构性较素红黏土好。     

Carbonation processes in municipal solid waste incinerator bottom ash and their effect on the leaching of copper and molybdenum

The interaction of CO₂ with municipal solid waste incinerator (MSWI) bottom ash was studied in order to investigate the resulting changes in pH and bottom ash mineralogy and the impact that these changes have on the mobility of Cu and Mo. Carefully controlled carbonation experiments were performed on bottom ash suspensions and on filtered bottom ash leachates. Changes in leachate composition were interpreted with the geochemical model MINTEQA2, and neoformed minerals were investigated by means of chemical and spectroscopic analysis. The leaching of Cu and Mo during artificial carbonation is compared to the leachability of Cu and Mo from a sample of naturally carbonated bottom ash from the same incinerator. During carbonation in the laboratory, a precipitate was formed that consisted mainly of Al-rich amorphous material, calcite, and possibly gibbsite. Carbonation to pH ≈8.3 resulted in a reduction of more than 50% in Cu leaching, and a reduction of less than 3% in Mo leaching. The reduction in Cu leaching is attributed to sorption to the neoformed amorphous Al-minerals. During natural weathering/carbonation of bottom ash, additional sorption sites are formed which further reduce the leaching of Cu and Mo on a time scale of months to years.     

粉煤灰作为路堤填料的动力特性试验研究

粉煤灰用作路堤填料时,其动力特性是大家较为关注的问题。在扬州电厂粉煤灰动三轴试验的基础上,对影响粉煤灰动强度的若干影响因素进行了分析,对粉煤灰路堤在饱水条件下的抗液化性能进行了探讨。研究结果表明：振次、初始静应力水平、含水量等对粉煤灰的动强度都有显著的影响;粉煤灰路堤在饱水条件下的抗液化性能则与地震动峰值加速度、初始静应力水平等有密切关系。     

Acid leaching of ash and coal: Time dependence and trace element occurrences

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.     

Geotechnical characterization of fly ash composites for backfilling mine voids

Backfilling of mine voids is mandatory to avoid subsequent ground stability problems in the form of subsidence. River sand and mill tailings have been widely used since a long time as backfilling materials. However, with a strict regulation banning river sand mining in India, research for developing alternative engineering materials substituting sand has gained importance. In the present study four fly ash composite materials (FCMs) was developed from the fly ash obtained from a captive thermal unit of Rourkela Steel Plant (RSP). The main constituent of the composite were fly ash, lime and gypsum. Detailed physical, and engineering properties were determined for the FCMs. Significant increases in the compressive strength were obtained after 56 days of curing time. A detailed SEM studies was undertaken to account for the increase in strength with time. The fly ash composite developed from RSP has potential to be used as substitute to sand for backfilling the mine voids.     

Performance of dry-separation processes in the recovery of cenospheres from fly ash and their implementation in a recovery unit

Cenospheres recovery is one of the coal fly ash beneficiations, providing economic as well as environmental benefits. Current techniques, such as lagoon or other wet-separation processes, consume large amounts of water and add to water pollution due to leaching of toxic materials from fly ash. The other possible disadvantage is the need for a wide operational area, which is unsuitable for densely populated countries. As wet-separation processes have some disadvantages, an improved and/or sustainable alternative recovery technique is required. An air classifier is one of the alternative techniques. In this study, two types of air classifiers, namely a closed-type pneumatic separator and a micron separator, have been investigated. In terms of separation efficiency, it was found that the micron separator has the potential to be applied in cenospheres recovery from coal fly ash, giving a Newton's efficiency of 0.44, as compared to a value of about 0.26 for the closed-type pneumatic separator. The cenospheres recoveries of both pieces of equipment at their optimum Newton's efficiencies were similar at over 60 wt.%. The separation performance was further assessed from the particle distributions of the overflow and underflow products obtained from both pieces of equipment, as well as from SEM images. It was found that the lower Newton's efficiency of the closed-type pneumatic separator was due to the re-concentration of fine particles in the underflow product at air-flow rates higher than 2.2 m/s (the underflow product yield was about 55 wt.%).In order to further confirm the applicability of this technique, the micron separator, which had provided higher separation efficiency and cenospheres recovery, was deployed in a cenospheres recovery unit prior to the use of a wet-separation process (float and sink tank). About 80% of the cenospheres was recovered, with an 87.8% reduction in the total mass of fly ash to be separated in the float and sink tank. Consequently, much less water was needed for the process of cenospheres recovery. Moreover, it was also confirmed that the micron separator could yield higher quality fly ashes, that is, fly ash types I and II, from lower feed quality of fly ash type IV, which is the lowest category in commercial classification of fly ash according to JIS A6201.     

Mineralogical and chemical composition of magnetic fly ash fraction

Magnetic fractions of coal fly ashes from three power plants were obtained by wet magnetic separation method. Quartz and mullite were the crystalline minerals dominating the nonmagnetic fractions. Magnetic fractions contained magnetite, hematite, and, to a lesser extent, quartz and mullite. Iron speciation by Mössbauer spectroscopy indicated the presence of Fe²⁺ and Fe³⁺ in aluminosilicate glass in magnetic fractions apart from magnetite and hematite. Chemical analyses revealed that magnetic fractions had about 2.5 times higher concentrations of Co and one to two times higher concentrations of Ni, Cu, Zn, Mo, and Cd. The dominant magnetic minerals were ferrimagnetic, and multi domain and stable single domain grains contributed mainly to the magnetic enhancement of fly ash samples.     

Formation and kinetics of porous cordierite from fly ash

Porous cordierite ceramics were prepared from a mixture of coal fly ash and basic magnesium carbonate at 1100-1350℃. Porosity, flexural strength and thermal expansion coefficient of the samples sintered at 1300℃ were estimated to be 26%, 65 MPa and 4.21×10^-6/℃, respectively. The kinetics of the formation progress was investigated by stepwise isothermal dilatometry （SID） accompanied with XRD, SEM and porosity measurement. It was found that the isothermal shrinkage data from SID could be well analyzed to get kinetic parameters according to the erapirical rate equation developed by Makipirtti-Meng, dY/dt=nk（T）Y（1-Y）（Y/1-Y）^（1/n）,where Y is the fractional shrinkage during the sintering process and n is a dimensionless component. The apparent activation energy △E values for 900-1000℃ and 1050-1 150℃ were 1294 and 1778 kJ/mol, respectively.     

不同压实度和基质吸力的粉煤灰三轴试验研究

粉煤灰的非饱和抗剪强度是准确分析非饱和状态灰坝的稳定性所必需的,但目前对其研究积累较少。通过控制不同压实度、不同基质吸力、不同净围压对粉煤灰进行一系列非饱和土三轴试验,探讨压实度和基质吸力对粉煤灰应力?应变关系曲线和强度参数的影响。研究结果表明,基质吸力较低时粉煤灰的应力?应变曲线没有峰值,呈硬化型;基质吸力逐渐增大时应力?应变曲线有明显的峰值,呈软化型;压实度越大,非饱和粉煤灰试样的应力?应变曲线的软化特征越明显,总黏聚力和内摩擦角均越大;非饱和粉煤灰的总黏聚力随着基质吸力的增大而逐渐增大,增大速率逐渐变缓,最后趋于稳定;不同基质吸力粉煤灰试样的内摩擦角变化不大,并且都近似等于饱和试样的内摩擦角;随着基质吸力的增大,吸力内摩擦角对粉煤灰试样的抗剪强度的贡献越来越小。研究得出的非饱和粉煤灰的抗剪强度特性对灰坝的设计和稳定性分析具有理论意义和工程实用价值。     

Mercury capture by selected Bulgarian fly ashes: Influence of coal rank and fly ash carbon pore structure on capture efficiency

Mercury capture by fly ash C was investigated at five lignite- and subbituminous-coal-burning Bulgarian power plants (Republika, Bobov Dol, Maritza East 2, Maritza East 3, and Sliven). Although the C content of the ashes is low, never exceeding 1.6%, the Hg capture on a unit C basis demonstrates that the low-rank-coal-derived fly ash carbons are more efficient in capturing Hg than fly ash carbons from bituminous-fired power plants. While some low-C and low-Hg fly ashes do not reveal any trends of Hg versus C, the 2nd and, in particular, the 3rd electrostatic precipitator (ESP) rows at the Republika power plant do have sufficient fly ash C range and experience flue gas sufficiently cool to capture measurable amounts of Hg. The Republika 3rd ESP row exhibits an increase in Hg with increasing C, as observed in other power plants, for example, in Kentucky power plants burning Appalachian-sourced bituminous coals. Mercury/C decreases with an increase in fly ash C, suggesting that some of the C is isolated from the flue gas stream and does not contribute to Hg capture. Mercury capture increases with an increase in Brunauer-Emmett-Teller (BET) surface area and micropore surface area. The differences in Hg capture between the Bulgarian plants burning low-rank coal and high volatile bituminous-fed Kentucky power plants suggests that the variations in C forms resulting from the combustion of the different ranks also influence the efficiency of Hg capture.     

Fractal kinetic characteristics for dissolving and leaching processes of strontium residue

The pore structural characteristics of strontium residue were studied with the N₂ adsorption method (ASAP2010). The kinetic properties concerning dissolving and leaching strontium waste were described by determining the concentrations of Sr²⁺, Ba²⁺ and soluble sulphides in solutions. The results showed that the specific surface area and pore volume increased with decreasing granule diameter, and the micropore surface of the residue was fractal. In the dissolving and leaching processes of strontium residue, soluble ion concentrations increased with decreasing granule diameter of the residue, and the reaction dimension was lower than the fractal dimension of pore surface. Sr²⁺ and soluble sulphide concentrations significantly exceeded the defined standard values, while Ba²⁺ concentrations did not, either in the dissolving or leaching solutions. In addition, dissolving and leaching reactions selectively occurred on the micropore surface of strontium residue.     

Effects of alkaline-activated fly ash and Portland cement on soft soil stabilisation

This paper studies the effects of sodium-based alkaline activators and class F fly ash on soil stabilisation. Using the unconfined compressive strength test (UCS), the effectiveness of this binder is compared with that of a common cement-based binder. Influence of the activator/ash ratio, sodium oxide/ash ratio and sodium hydroxide concentration was also analysed. Sodium hydroxide concentrations of 10, 12.5 and 15 molal were used for the alkaline-activated specimens (AA), with activator/ash ratios between 1 and 2.5 and ash percentages of 20, 30 and 40 %, relatively to the total solids (soil + ash). UCS was determined at curing periods of 7, 28, 90 and 365 days, and the most effective mixtures were analysed for mineralogy with XRD. The results showed a clear increase in strength with decreasing activator/ash ratio (up to a maximum of 43.4 MPa), which is a positive result since the activator is the most expensive component in the mixture. Finally, UCS results of the cement and AA samples, at 28 days curing, were very similar. However, AA results proved to be just between 20 and 40 % of the maximum UCS obtained at 1 year curing, while cement results at 28 days are expected to be between 80 and 90 % of its maximum.     

Long-term brine impacted fly ash,Part II: Mobility of major species in the ash residues

The leaching of major species from fly ash is a function of the pH of the solution in contact with the fly ash. The aim of this study was to determine the effect of the pH of the leachant on the leaching of species from the ash residues recovered after the long-term fly ash–brine interactions. Acid neutralization capacity (ANC) tests using solutions of different pH values ranging from the initial pH of the ash residues (11–12) to pH 4 were employed in the leaching experiments. The ANC tests revealed that the release of major species from the ash residues depended on the pH of the leachants except for Na and Cl, where the significant concentrations leached were independent of the solution pH. The concentrations of Al and Si in the ANC leachates were very high at pH below 6 while Ca, K, Sr, Mg and B were immediately mobilized from the brine impacted fly ash when in contact with de-ionized water, and leaching increased as the pH decreased. The concentration of SO₄ leached from the brine impacted ash residues at high pH was high, and the leaching increased with decrease in the pH of the leachant. This study shows that most of the major elements captured in the ash residues could be mobilized when in contact with aqueous solutions of various pH. This reveals that the co-disposal of fly ash and brine may not be the best practice as the major elements captured in the ash residues could leach over time.     

大掺量粉煤灰淤泥固化土的强度与耐久性研究

基于传统水泥和石灰固化处理方法,提出了利用大掺量低钙粉煤灰、水泥和石灰固化剂进行淤泥固化处理的方法,以期改善淤泥的强度和耐久性,达到淤泥和粉煤灰双重资源化利用的目的。通过一系列室内试验,探讨了该方法处理后固化淤泥的击实特征、强度特性、水稳性和耐久性。试验结果表明：淤泥固化后最优含水率有所降低、最大干密度则略有增加;弹性模量、无侧限抗压强度和抗拉强度均有不同程度的增加,水泥掺量越大,养护时间越长,强度和弹性模量越大;固化后淤泥水稳性得到明显改善;浸水软化和冻融循环导致固化土抗压强度显著劣化,冻胀融缩导致设计混合料的无侧限抗压强度减小约22%。