Utilization of fly ash in adsorption of heavy metals from wastewater

The aim of this study was to assess the toxicity reduction of wastewaster after treatment with fly ash. Fly ash is a waste material which is formed as a result of coal burning in power plants, but has the potential to adsorb heavy metal ions. The present study examined the adsorption capacity of fly ash to adsorb Pb²⁺, Cu²⁺, and Zn²⁺ from waste water under different conditions of contact time, pH, and temperature. Uptake of metal ions by fly ash generally rose with increasing pH. At lower temperatures the uptake of heavy metal adsorption were enhanced. Significant reduction in Pb²⁺ (79%), Cu²⁺ (53%), and Zn²⁺ (80%) content was found after treatment with fly ash of waste water treatment. Using the microtox test toxicity of the effluent was reduced by 75% due to removal of Pb²⁺ ion by the fly ash. Data indicated that fly ash generated by power plants may be used beneficially to remove metals from waste water.     

不同粒径垃圾焚烧飞灰中重金属富集特性表征

针对杭州市生活垃圾焚烧飞灰按粒径级别进行其重金属特性表征,主要展开飞灰组成元素和矿物成分、重金属含量分布、以及重金属与飞灰颗粒的微观结合行为等研究.结果表明,＂SiO2-CaO-Al2O3-金属氧化物＂体系构成了重金属的富集载体;Zn、Pb、Cu、Mn、Ni、Cr、Sb等重金属在75—125μm飞灰颗粒中的占有率最高,达52%;Zn、Cu、Cr随着粒径减小其含量显著增加,其它重金属未见此趋势;通过SEM-EDX对飞灰颗粒表面和断面进行扫描电镜观察和面、线扫描元素能谱分析,在飞灰断面发现了更多类型、更密集的重金属分布.通过结合XRF、ICP-MS、SEM-EDX等仪器手段分析飞灰中重金属富集特性,深入探索重金属在飞灰颗粒中富集特征.     

Treatment of dyeing wastewater using coal fly ash as co-coagulant

This article deals with the co-coagulation of dyeing wastewater by coal fly ash using FeSO₄ as coagulant, Benzo Scarlet 4BS and Brilliant Acid Scarlet 3R as the testing dyes. The optimal concentration of FeSO₄ for co-coagulation process is 0.6–0.8?g/L wastewater, and the concentration of fly ash 4–5?g/L. The experimental results show that the co-coagulation process by fly ash helps to improve the color reduction, greatly accelerate the formation and settling of the floc, and reduce the content of the floc. The mechanism for co-coagulation process is discussed and similar effect is obtained when the co-coagulation method is applied for the treatment of the real dyeing wastewater samples.     

Recovery of molybdenum from fly ash by gibbsite

The effectiveness of gibbsite (GB), an amorphous aluminum oxide, for the recovery of Mo(VI) from eluates of fly ash of two coal-fired thermal power stations and of roof tile waste was investigated. Upon the qualitative analysis of an eluate of fly ash, 16 elements were detected. Greater amounts of these elements were eluted under acidic conditions (pH 2) than from the neutral or basic eluate of fly ash. GB was used for the adsorption of Mo(VI). Equilibrium adsorption was reached within 1?min. Optimal solution acidity for the adsorption of Mo(VI) onto GB400 (calcined at 400°C) was pH 2. The main adsorption mechanism was ion exchange with a number of hydroxyl groups of GB400. For repeated ad- and desorption of Mo(VI), GB400 could be used at least four times and the recovery percentage of Mo(VI) with sodium hydroxide solution as eluent surpassed 90%. Our results showed that GB400 was very effective for the recovery of Mo(VI) from fly ash.     

红枫湖水源地附近粉煤灰堆积场重金属存在形态及静态淋溶规律

酸雨对露天粉煤灰堆积场的淋滤作用导致周围环境产生重金属污染是一种广泛现象.为研究酸雨对贵阳市水源地红枫湖周边一大型粉煤灰堆积场的重金属迁移影响,本文以这一粉煤灰堆积场为研究对象,通过静态淋溶实验探讨了粉煤灰中Cr、Ni、CU、Zn、AS、Cd、Pb等7种重金属元素的含量、存在形态、淋溶时间、堆积时间、粒度对重金属溶出规律的影响.结果表明,粉煤灰中Ni、Cu、Zn、Pb、As和Cd等6种重金属的含量随堆积时间增加而增大,Cr含量变化与上述反之;在淋溶实验中,堆积时间的增加使Cr、Ni、Cu和Zn重金属元素的可溶态减小;在淋溶第28—48天期间,Cr、Ni和Cu元素溶出浓度降低的粒度顺序为细粒度>中粒度和粗粒度、Cd元素溶出浓度降低的粒度顺序为中粒度>粗粒度>细粒度.本研究对红枫湖水源地和周边地下水的重金属防控提供一定的参考依据.     

Characteristics of the stabilized/solidified municipal solid wastes incineration fly ash and the leaching behavior of Cr and Pb

Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure.     

Effect of seawater salinity on the synthesis of zeolite from coal fly ash

A novel method for the synthesis of zeolite was developed in this paper. The synthesis was carried out by hydrothermal activation after alkali fusion and coal fly ash （CFA） was used as raw material with seawater of different salinities. Seawater salinity was varied from 32 to 88 for zeolite crystallization during the hydrothermal process. The results show that seawater salinity plays an important role in zeolite synthesis with CFA during hydrothermal treatment. The products were a mixture of NaX zeolite and hydroxysodalite; seawater salinity more strongly affected the crystallization than the type and chemical composition of the zeolites. The yield of CFA transformed into zeolite gradually rose with the increase in salinity, reaching a transformation rate of 48%--62% as the salinity increased from 32 to 88, respectively. The proposed method allows for the efficient disposal of by-products; therefore, the application of seawater in zeolite synthesis presents promising economic and ecological benefits.     

Hydrothermal treatment of MSWI fly ash for simultaneous dioxins decomposition and heavy metal stabilization

Researches on the hydrothermal treatment of municipal solid waste incineration (MSWI) fly ash were conducted to eliminate dioxins and stabilize heavy metals. In order to enhance decomposing polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) during hydrothermal process, a strong reductant carbohydrazide (CHZ) is introduced. A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature; CHZ was spiked into solution according to specially defined dosage. Experimental results showed that under the temperatures of 518 K and 533 K, the decomposition rates of PCDDs/PCDFs were over 80% and 90%, respectively, by total concentration. However, their toxic equivalent (TEQ) decreased only slightly or even increased due to the rising in concentration of congeners 2, 3, 7, 8-TCDD/TCDF, which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process. Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results. Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.     

Trace element uptake in plants grown on fly ash amended soils

Four crop plants were grown in a greenhouse in soils amended with 0, 5, 10, and 20% by weight of coal combustion fly ash to evaluate potential trace element uptake by the vegetation. The leaves and stems from each plant were harvested and analyzed for As, Cd, Co, Cu, Mn, Mo, Pb, Se, Tl, and Zn content during early, middle, and late growth. The trace element data were statistically analyzed using Analysis of Variance (ANOVA) to determine whether the trace element uptake in the four crop plants differed significantly between the soil treatments, and to identify significant differences in trace element uptake through time. The results show that the amount of amended fly ash does not significantly influence the concentration of most trace elements in plant tissue, and that some concentrations actually decrease with time. Although this study did not find a significant increase in trace element uptake, care must be taken in a natural environment where plants may behave differently.     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

PCDD/DFs and coplanar PCBs in fly ash samples from various types of incinerators in Taiwan

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/DFs) and coplanar polychlorinated biphenyls (Co‐PCBs) were determined in fly ash samples from municipal solid waste (MSW), medical waste (MW), and electricity power plant incinerators in Taiwan. The average concentrations of PCDD/DFs and Co‐PCBs are 7.02 ng‐TEQ/g and 1.06 ng‐TEQ/g, respectively. The contributions to total TEQ are 24% from PCDDs, 64% from PCDFs, and 12% from Co‐PCBs, indicating that PCDFs generate the highest environmental impact and MSW and MW incinerators are potential Co‐PCBs contaminating sources. The levels of PCDD/DFs and Co‐PCBs found in ash samples increase from petroleum‐fired, coal‐fired, large municipal solid waste, small medical waste, to small municipal solid waste incinerators, and are generally lower than those from incinerators built earlier. All fly ash samples analyzed in this study were considered hazardous materials. More research is suggested to establish the relationship between the amounts of PCDD/DFs and Co‐PCBs in fly ash and in flue gas.     

Effects of sulfur on variations in the chemical speciation of heavy metals from fly ash glass

● A higher sulfur content reduced the curing rate of Cr in glass. ● Depolymerization increased the amounts of heavy metals in the carbonate bound state. ● Reducing the CaO/SiO₂ ratio increased the proportion of stable heavy metals. This work designed a new CaO-Al₂O₃-SiO₂-SO₃ glass for the immobilization of multiple heavy metals found in dechlorinated fly ash having high amounts of calcium and sulfur. Increasing the (CaO + SO₃)/SiO₂ mass ratio (M(CS/S)) from 0.28 to 0.85 was found to lower the proportions of Mn, Ni and Zn in an unstable state, while an M(CS/S) ratio of 0.51 gave the lowest proportions of unstable Cr and Pb. Decreasing the degree of polymerization of the glassy network increased the proportions of Mn, Cr, Ni, Pb and Zn in the carbonate bound state. The leaching out of metals in this state was the primary cause of degradation of Q³ structural units in the glassy network. The amount of Mn in the iron-manganese oxide bound state was increased by increasing the number of Q² units in the silicate network. Decreasing the CaO/SiO₂ mass ratio (M(C/S)) raised the proportions of Mn, Ni and Zn in the unstable state. An M(C/S) value of 0.43 lowered the proportions of unstable Cr and Pb. A principal components analysis determined that the leaching of toxic heavy metals from the glass was primarily related to the proportions of these metals in the unstable state while there were no evident correlations between leaching and the proportions in stable states.     

城市垃圾焚烧飞灰中重金属的形态及酸浸出性研究

研究了城市垃圾焚烧飞灰中重金属形态在不同粒径上的分布,以及HNO3对飞灰中重金属的浸出性.结果表明:飞灰中重金属主要以残渣态存在,可交换离子态含量很少;易挥发性的重金属在较大粒径上有较高分布,亲石性重金属Cr和Ni的分布与粒径的相关性不大,在各粒径上的分布较均匀;飞灰中以碳酸盐结合态存在的重金属对酸不稳定,易被HNO3浸出,而残渣态部分对酸较稳定,不易被HNO3浸出.     

Disposal of Coal Fly Ash at A Deep Water Site in the Eastern Mediterranean Off Israel - Six Years of Monitoring

Coal fly ash (CFA) is dumped at a deep sea disposal site (1,500m water depth) in the eastern Mediterranean, ca. 70km off the Israeli shore. Since 1989, about one million tons of CFA were dumped at the 200km² allocated area. Six years of monitoring at the dump-site shows that the CFA is heterogeneously distributed; there are areas where CFA covers about 1.3cm depth of the sea floor while at others no CFA is found. CFA is present as a fine powder, small aggregates and even as large blocks both in the dump-site as well as at its peripheries. Cadmium, copper and zinc concentrations in the CFA decreased as a result of the prolonged contact with sea water at in situ conditions while inconclusive changes in mercury, iron and manganese were detected. No changes were observed for lead, iron and aluminium concentrations. A controlled long term field experiment, now in progress at the site, is expected to clarify further chemical changes occurring in the CFA.     

Disposal of Coal Fly Ash at A Deep Water Site in the Eastern Mediterranean Off Israel - Six Years of Monitoring

Coal fly ash (CFA) is dumped at a deep sea disposal site (1,500m water depth) in the eastern Mediterranean, ca. 70km off the Israeli shore. Since 1989, about one million tons of CFA were dumped at the 200km² allocated area. Six years of monitoring at the dump-site shows that the CFA is heterogeneously distributed; there are areas where CFA covers about 1.3cm depth of the sea floor while at others no CFA is found. CFA is present as a fine powder, small aggregates and even as large blocks both in the dump-site as well as at its peripheries. Cadmium, copper and zinc concentrations in the CFA decreased as a result of the prolonged contact with sea water at in situ conditions while inconclusive changes in mercury, iron and manganese were detected. No changes were observed for lead, iron and aluminium concentrations. A controlled long term field experiment, now in progress at the site, is expected to clarify further chemical changes occurring in the CFA.     

Porous silica synthesis out of coal fly ash with no residue generation and complete silicon separation

● Both amorphous and crystalline silicon are completely separated from coal fly ash. ● Porous silica is synthesized out of coal fly ash. ● No residues is produced during the whole synthesis process. ● The one-step method to synthesize silica don’t need long-time reaction and aging. Ordered mesoporous silica materials exhibit enormous potential in industrial production. Since coal fly ash (CFA) is abundant in Si, it has become a green and promising way to utilize CFA by synthesizing porous silica materials. However, the stable crystalline structure of CFA limits the extraction of Si, and the residue is generated during the process of extracting Si. In this work, we proposed a no-residue method to synthesize ordered mesoporous silica out of CFA. Sodium carbonate (Na₂CO₃) was used to reconstruct the crystals of the CFA, and the calcined mixture then directly reacted with the precipitators. This method combined the process of Si extraction and porous material synthesis. In this method, no residue was generated and the silicon in both amorphous and crystalline phases of CFA was fully utilized. By this method, the extraction efficiency of Si was increased from 31.75% to nearly 100%. The as-synthesized mesoporous silica had a highly-ordered pore structure with a space group of la-3d, a surface area of 663.87 m²/g, a pore volume of 0.41 cm³/g, and an average pore diameter of 2.73 nm. The mechanism of crystalline transformation and material structure formation were systematically studied. This method provides a new idea to dispose of CFA and synthesize porous silica materials.     

粉煤灰资源的农业利用

本文根据粉煤灰农业利用的基础及国内外研究现状，阐述了粉煤灰农业利用现状，包括直接施用于农田、利用粉煤灰生产化肥、贮灰场覆土或不覆土造田和填坑造地等。并对粉煤灰农业利用的前景提出了一些看法。     

Levels and patterns of polychlorinated biphenyls in residues from incineration of established source-classified MSW in China

Municipal solid waste (MSW) source-classified collection represents an advancement in resource cycling and secondary pollution control in China. Comparative experiments were performed to assess the levels and patterns of polychlorinated biphenyls in bottom ash, fly ash from boiler, and fly ash from bag filter from an MSW incineration plant with source-classified collection of MSW. Polychlorinated biphenyls were concentrated in the bag filter fly ash and in the bottom ash. The total amount of polychlorinated biphenyls was much lower than in fly ashes and bottom ash from traditional mixed waste incineration. Total concentration of coplanar polychlorinated biphenyls and toxic equivalent quantities were also reduced. Due to variations of feed waste, complete combustion, including continuously high incineration temperature, low CO concentrations and high air excess ratio were observed. Incineration temperature showed a negative correlation, while CO concentration showed a positive correlation with total and coplanar polychlorinated biphenyls, indicating that the latter can be reduced by controlling combustion conditions related to properties of feed waste.     

Lung retention and bioavailability of arsenic after single intratracheal administration of sodium arsenite,sodium arsenate,fly ash and copper smelter dust in the hamster

Arsenic is present in airborne particulate material released by coal-fired power plants and non-ferrous metal smelters. We have assessed whether the physico-chemical properties of arsenic in such particles play a role in its lung retention and uptake by the body. Female hamsters were given a single intratracheal instillation of fly ash or copper smelter dust suspensions (at doses of 50 or 100 g As kg^–1) or identical amounts of soluble tri- and pentavalent arsenic, in the presence or absence of an inert dust material (tungsten carbide). The concentration of the element was measured in a 24 hour urine sample collected on the 1st, 2nd and 6th day after treatment and arsenic remaining in lung tissue was determined at the end of the same time periods. Both lung retention and urinary As excretion indicate a prolonged contact of the lung tissue with particulate As in contrast to soluble As salts. In addition to the effect of solubility described here, more research is needed to determine the effect of particle size and lung loading on retention, as well as the potential differences in the lung inflammatory response using arsenic-rich particulates from various sources.