Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.     

Leaching characteristics of residual lateritic soils stabilised with fly ash and lime for geotechnical applications

The effective use of residual lateritic soils as fill material for various construction activities is often limited by the difficulty in handling them. Attempt to improve their workability with fly ash and lime has shown promising results, although accompanied by risk of release of heavy metal leachates to the groundwater. In the present work, the leaching properties from residual lateritic soils from a part of Northeast India stabilised with fly ash and lime (CaO) was investigated with the help of single batch leaching test and column leaching test for different soil-fly ash-lime mixes. Test results show that the high pH induced by lime treatment of the mixes helps in keeping most of the metals within the stabilised soil matrix. Although the heavy metal concentrations in the leachates were generally within permissible limits, the release response for different metals was different suggesting implications for permeate solutions having metal pre-concentrations, such as those emanating from hazardous landfill sites. The observed characteristics provide insights towards the potential and realistic estimates of leaching of metals and its variation due to change in fly ash and lime content in the stabilised mix. Many of these constituents found in the stabilised soil had a first-flush phenomenon. But, as they occur only for short duration (about 5 pore volumes over 5 days) and at low concentration, dilution effect may eliminate them. The effect of continuous permeation on the flow parameters and the leaching pattern of the mixes have also been highlighted.     

生物质直接燃烧发电技术的探索

介绍了生物质直接燃烧发电技术原理及其设备的工作过程,着重讨论了生物质锅炉燃烧过程中的燃料收集和存储、送料堵塞以及受热面结焦等问题,并提出了优化运行和提高锅炉效率的改进措施。     

Humification index of composts originating from three types of woody biomass

Composting is a good method for recycling surplus manure and stabilizing organic matter from biowastes. Compost is used as a soil amendment and recently, for restoration of vegetation in barren areas. We investigated the relationship between the type of woody biomass (using Robinia pseudoacacia, Japanese larch and apple) and the humification index (HI) of the resulting compost. This study evaluated the difference in HI between the three compost types, and the structural features of composts and extracted humic acids (HAs). The HIs for R. pseudoacacia and apple were larger than that for Japanese larch after composting for 11 months. The structural features of the Japanese larch compost were also different from the apple and R. pseudoacacia, with a very high carbon/nitrogen ratio. The average molecular weights and ultraviolet–visible spectra (A600/C) of HAs extracted from composting samples at 0 and 11 months indicate that the humification rate of Japanese larch was slower than that of R. pseudoacacia and apple. During composting, the average molecular weights of apple and R. pseudoacacia decreased, while their A600/C values increased, but the reverse was observed for Japanese larch. The humification rate was found to depend on the type of woody biomass being composted.     

Leaching behaviour of bottom ash from RDF high-temperature gasification plants

This study investigated the physical properties, the chemical composition and the leaching behaviour of two bottom ash (BA) samples from two different refuse derived fuel high-temperature gasification plants, as a function of particle size. The X-ray diffraction patterns showed that the materials contained large amounts of glass. This aspect was also confirmed by the results of availability and ANC leaching tests. Chemical composition indicated that Fe, Mn, Cu and Cr were the most abundant metals, with a slight enrichment in the finest fractions.Suitability of samples for inert waste landfilling and reuse was evaluated through the leaching test EN 12457-2. In one sample the concentration of all metals was below the limit set by law, while limits were exceeded for Cu, Cr and Ni in the other sample, where the finest fraction showed to give the main contribution to leaching of Cu and Ni.Preliminary results of physical and geotechnical characterisation indicated the suitability of vitrified BA for reuse in the field of civil engineering. The possible application of a size separation pre-treatment in order to improve the chemical characteristics of the materials was also discussed.     

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.     

低温热解生物质与煤共燃的污染性能和经济性能评价

在简要说明生物质与煤共燃意义的基础上,对低温热解生物质和煤共燃的污染性能和经济性能进行了研究和评价.认为低温热解生物质(锯屑、谷壳和花生壳)与煤共燃能够减排CO2、CH4等温室气体及NOX和SO2等大气污染物,减排重金属污染物和其它微量有毒有害元素;同时,二者共燃可以在运输成本、存储成本、电厂生物质处理费用、设备改造费用和节约煤炭等方面降低电厂的运营成本,但也可能在生物质低温热解产品加工上提高生产费用以及在因燃用热解生物质可能造成的积灰结渣上提高设备维护费用.可以预见,生物质与煤共燃的研究将是实现能源可持续发展的有效措施之一.     

Leaching toxicity and heavy metal bioavailability of medical waste incineration fly ash

The aim of this study was to provide a comprehensive risk assessment for medical waste incineration fly ash from another aspect through various leaching methods. The differences and connections between leaching concentrations achieved via the toxicity characteristic leaching procedure (TCLP), the physiologically based extraction test (PBET) and the sequential extraction procedure were also described. Heavy metal contents of the used medical waste incineration fly ash were 1.7–31 times higher than that from Japan, indicating poor medical waste management in China. The fly ash leaching concentration in the TCLP test exceeded the regulation value and can be characterized as hazardous waste under current regulations. However, the PBET concentrations were only 1/10 of the TCLP value or even lower, and the calculated ingested contents of all heavy metals were lower than tolerable daily intake, demonstrating that TCLP might have overestimated the environment risk to some degree. The leaching metal content of TCLP ranged from exchangeable to residual forms, and the leaching percentage varied from 7.75 to 92.55 %, while the content for PBET was equal to or lower than the exchangeable form.     

Comparative study on the characteristics of fly ash and bottom ash geopolymers

This research was conducted to compare geopolymers made from fly ash and ground bottom ash. Sodium hydroxide (NaOH) and sodium silicate (Na(2)SiO(3)) solutions were used as activators. A mass ratio of 1.5 Na(2)SiO(3)/NaOH and three concentrations of NaOH (5, 10, and 15M) were used; the geopolymers were cured at 65 degrees C for 48 h. A Fourier transform infrared spectrometer (FT-IR), differential scanning calorimeter (DSC), and scanning electron microscope (SEM) were used on the geopolymer pastes. Geopolymer mortars were also prepared in order to investigate compressive strength. The results show that both fly ash and bottom ash can be utilized as source materials for the production of geopolymers. The properties of the geopolymers are dependent on source materials and the NaOH concentration. Fly ash is more reactive and produces a higher degree of geopolymerization in comparison with bottom ash. The moderate NaOH concentration of 10 M is found to be suitable and gives fly ash and bottom ash geopolymer mortars with compressive strengths of 35 and 18 MPa.     

Leaching behavior of polychlorinated dibenzo-p-dioxins and furans from the fly ash and bottom ash of a municipal solid waste incinerator

The leaching behavior of dioxins from landfill containing bottom ash and fly ash from municipal solid waste incineration has been investigated by leaching tests with pure water, non-ionic surfactant solutions, ethanol solutions, or acetic acid solutions as elution solvents for a large-scale cylindrical column packed with ash. Larger amounts of dioxins were eluted from both bottom ash and fly ash with ethanol solution and acetic acid solution than with pure water. Large quantities of dioxins were leached from fly ash but not bottom ash by non-ionic surfactant solutions. The patterns of distribution of the dioxin congeners in the leachates were very similar to those in the bottom ash or fly ash from which they were derived.     

Leaching from MSWI bottom ash: evaluation of non-equilibrium in column percolation experiments

Impacts of non-equilibrium on results of percolation experiments on municipal solid waste incineration (MSWI) bottom ash were investigated. Three parallel column experiments were performed: two columns with undisturbed percolation and one column with two sets of 1-month-long flow interruptions applied at liquid-to-solid (L/S) ratios of L/S 2L/kg and 12L/kg, respectively. Concentrations of Na, K, Cl(-), Ca, Si, SO(4)(2-), Al, Cu, Ni, Mo, Ba, Pb, Zn, and dissolved organic carbon (DOC) were monitored throughout the entire leaching period; geochemical modeling was used to identify non-equilibrium-induced changes in the solubility control. Despite both physical and chemical non-equilibrium, the columns were found to provide adequate information for readily soluble compounds (i.e., Na, Cl(-), and K) and solubility-controlled elements (i.e., Ca, SO(4)(2-), Ba, Si, Al, Zn, and Pb). The leaching of Cu and Ni was shown to depend strongly on DOC leaching, which was likely affected by physical non-equilibrium during flow interruptions. Consequently, the leaching of Cu and Ni in the undisturbed columns was shown to be by about one order of magnitude lower compared with the interrupted column. The results indicate that the leaching of DOC-related metals in laboratory column experiments may be considerably underestimated compared with full-scale scenarios in which the impacts from non-equilibrium may be significantly lower. The leaching of Mo (or MoO(4)(2-)) may be controlled solely by its availability in the mobile zone, which in turn appeared to be controlled by diffusion from the stagnant zone; no Mo controlling minerals were predicted by the geochemical modeling.     

燃煤飞灰中痕量元素的研究

综述了煤中痕量元素的含量分布、煤燃烧过程中痕量元素的分布转化规律,总结了痕量元素在飞灰中的富集规律和赋存状态,以及痕量元素的释放控制方法和技术,并探讨了今后的研究方向.     

Characteristics variation of coal combustion residues in an Indian ash pond.

Coal-fired power plants all over the world are cited as one of the major sources that generate huge quantities of coal combustion residues (CCRs) as solid wastes. Most frequently CCRs are collected through electrostatic precipitators, mixed with bottom ash by hydraulic systems and deposited in ash ponds. The quality of the CCRs at different locations in one of the ash ponds in Central India was evaluated to understand the variation in characteristics with a view to effective utilization. Results revealed that the presence of fine particles (< 50 mocrom) increased with increasing distance from the ash slurry inlet zone in the ash pond. Wide variations in the bulk density (800-980 kg m(-3)), porosity (45-57%) and water-holding capacity (57.5-75.7%) of CCRs were recorded. With increasing distance the pH of the CCRs decreased (from 9.0 to 8.2) and electrical conductivity increased (from 0.25 to 0.65 dS m(-3)). The presence of almost all the heavy metals in CCRs exhibited an increase with distance from the ash slurry discharge zone due to the increase in surface area (from 0.1038 to 2.3076 m2 g(-1)) of CCRs particles. The present paper describes the variation of characteristics of CCRs deposited in the ash pond and their potential applications.     

Influence of waste input and combustion technology on MSWI bottom ash quality

The waste input and the process technology of waste incineration plants appear to have a great influence on bottom ash quality. To better understand how these parameters can affect the characteristics of residues, bottom ash from six plants were tested and compared in this study. Bottom ash physico-chemical characteristics were investigated by chemical analyses, and leaching tests. In order to understand their long-term behavior, accelerated ageing experiments and biodegradation tests were also performed. The whole analyses gave complementary information. It was shown that the six samples do have different properties. Waste inputs have a great influence on Cl and S content in bottom ash, as well as on the Ca/Si ratio. The importance of this ratio on the carbonation process has been demonstrated. Combustion parameters have an influence on the quantity and mobility of the residual organic matter.     

Leaching characteristics and phytotoxic effects of sewage sludge biochar

Biochar was prepared via the pyrolysis of sewage sludge at temperatures ranging from 300 to 900 °C and the physical–chemical compositions of the biochars obtained were analyzed. Leaching tests were conducted using the biochars to investigate the release of the constituents and their phytotoxic effects on wheat (Triticum aestivum) seeds in a germination test. Multivariate analyses were used to evaluate the contributions of the constituents to the germination index (GI). The results showed that the biochars were rich in micronutrient contents and they improved the germination of wheat. The heavy metal contents were higher in the biochars than the sewage sludge and their levels increased with the pyrolysis temperature, but they were within the acceptable limits for land application, thereby suggesting that sewage sludge is suitable for use as a biochar substrate. The different components of the biochar leachates could promote and inhibit the germination of wheat seeds, where the GI was promoted at lower concentrations but inhibited at higher concentrations. Our results suggest that biochar is an effective and environmentally friendly fixative for the immobilization of heavy metals in sewage sludge when applied to land or disposed of in landfill, but its ecotoxicity needs to be assessed to ensure its environmental safety.     

High temperature air-blown woody biomass gasification model for the estimation of an entrained down-flow gasifier

A high temperature air-blown gasification model for woody biomass is developed based on an air-blown gasification experiment. A high temperature air-blown gasification experiment on woody biomass in an entrained down-flow gasifier is carried out, and then the simple gasification model is developed based on the experimental results. In the experiment, air-blown gasification is conducted to demonstrate the behavior of this process. Pulverized wood is used as the gasification fuel, which is injected directly into the entrained down-flow gasifier by the pulverized wood banner. The pulverized wood is sieved through 60 mesh and supplied at rates of 19 and 27kg/h. The oxygen-carbon molar ratio (O/C) is employed as the operational condition instead of the air ratio. The maximum temperature achievable is over 1400K when the O/C is from 1.26 to 1.84. The results show that the gas composition is followed by the CO-shift reaction equilibrium. Therefore, the air-blown gasification model is developed based on the CO-shift reaction equilibrium. The simple gasification model agrees well with the experimental results. From calculations in large-scale units, the cold gas is able to achieve 80% efficiency in the air-blown gasification, when the woody biomass feedrate is over 1000kg/h and input air temperature is 700K.     

Treatment process for MSW combustion fly ash laboratory and pilot plant experiments

Fly ash from combustion of municipal solid waste sometimes contains large amounts of soluble salts, such as NaCl, even though the content of soluble toxic metal compounds is relatively low. Removal of the salts by washing with water has been suggested as a method to increase the stability of this type of ash. In the work presented here, a simple washing process was studied and evaluated. The process includes three steps: leaching with water, filtration and displacement washing. Basic data were obtained in laboratory experiments and used in the construction of pilot plant equipment at a full size fluidized bed boiler, where a side-stream of the cyclone ash was treated. The process was designed to minimize the water consumption while obtaining an effective removal of salts and a stable ash residue. In order to achieve this, recirculation of leaching liquor was used and the displacement washing was adjusted to become close to ideal. The results showed that an ash/water slurry with a liquid to solid ratio as low as 3 could be handled without difficulty in the mixing, pumping and filtration units. Washing of the filter cake at a liquid to solid ratio of 0.5 removed the major part of the remaining dissolved salts in the pore liquid. About 90% of the chloride content was removed from the ash, whereas the contents of Na, K, Ca, Cd, Pb and a number of other minor elements were removed by 10-30%. Before treatment, the results of ash leaching tests were sometimes too high for chloride (2003/33/EC), but the treatment reduced the amount of soluble chlorides to far below the limit values. The leachability of most metals was reduced or unaffected by the ash treatment. For Na, K and Cl, it was less than 10% of the value for the untreated ash. However, the results showed that some ash components may be mobilized by the washing. Antimony is the most important due to its toxicity.     

燃煤飞灰颗粒物中元素分布规律的研究

利用ICP-AES光谱仪和TOC总碳分析仪对不同粒级下的飞灰颗粒进行了元素测定,对元素分布规律的形成原因进行了分析.分析结果表明:煤经旋流燃烧器燃烧而未经过除尘设备的飞灰中300目以下小颗粒含量较高.随着燃烧温度的升高,大颗粒的含碳量增加,小颗粒的含碳量减少,元素Al、Mg、Cr在各个粒级中含量变化不大,Ti、Ba、V在大于280目的小颗粒中含量有下降趋势,其他大部分痕量元素在大于300目的小颗粒中得到富集.     

Reduction of CO2-emissions by using biomass in combustion and digestion plants

Climate protection is one of the main aims of environmental policy. One way to advance and push the progress is to reduce the use of fossil fuels for energy production through an increasing production of renewable and CO₂-neutral energy for example through application of biomass. This paper sets the focus on biomass streams that can be used both thermal and biological for energy production like grass or energy crops. To calculate the potentials of decrease of CO₂-emissions for treatment of biomass in either combustion or digestion plants some scenarios were set up with different assumptions regarding degree of efficiency of treatment plants which depends on size of plants and the treatment process itself. The energetic utilisation of the considered biomass streams is divided in different utilisation scenarios: combined heat and power generation (CHP) and heat generation or power generation only. Additionally four groups of plant sizes referring to electrical power (from 0.1 up to 10.0 MW) were taken into consideration. The calculations of potential savings of CO₂-emission in both types of treatment scenarios lead to the result that in comparison to biological technologies thermal processes show a much higher utilisation of the energy content in biomass.