Quantitative geochemical modelling using leaching tests: application for coal ashes produced by two South African thermal processes

The present work focuses on the reactivity of coal fly ash in aqueous solutions studied through geochemical modelling. The studied coal fly ashes originate from South African industrial sites. The adopted methodology is based on mineralogical analysis, laboratory leaching tests and geochemical modelling. A quantitative modelling approach is developed here in order to determine the quantities of different solid phases composing the coal fly ash. It employs a geochemical code (PHREEQC) and a numerical optimisation tool developed under MATLAB, by the intermediate of a coupling program. The experimental conditions are those of the laboratory leaching test, i.e. liquid/solid ratio of 10 L/kg and 48 h contact time. The simulation results compared with the experimental data demonstrate the feasibility of such approach, which is the scope of the present work. The perspective of the quantitative geochemical modelling is the waste reactivity prediction in different leaching conditions and time frames. This work is part of a largest research project initiated by Sasol and Eskom companies, the largest South African coal consumers, aiming to address the issue of waste management of coal combustion residues and the environmental impact assessment of coal ash disposal on land.     

Reduction of metal leaching in brown coal fly ash using geopolymers

Current regulations classify fly ash as a prescribed waste and prohibit its disposal in regular landfill. Treatment of the fly ash can reduce the leach rate of metals, and allow it to be disposed in less prescribed landfill. A geopolymer matrix was investigated as a potential stabilisation method for brown coal fly ash. Precipitator fly ash was obtained from electrostatic precipitators and leached fly ash was collected from ash disposal ponds, and leaching tests were conducted on both types of geopolymer stabilised fly ashes. The ratio of fly ash to geopolymer was varied to determine the effects of different compositions on leaching rates. Fourteen metals and heavy metals were targeted during the leaching tests and the results indicate that a geopolymer is effective at reducing the leach rates of many metals from the fly ash, such as calcium, arsenic, selenium, strontium and barium. The major element leachate concentrations obtained from leached fly ash were in general lower than that of precipitator fly ash. Conversely, heavy metal leachate concentrations were lower in precipitator fly ash than leached pond fly ash. The maximum addition of fly ash to this geopolymer was found to be 60wt% for fly ash obtained from the electrostatic precipitators and 70wt% for fly ash obtained from ash disposal ponds. The formation of geopolymer in the presence of fly ash was studied using 29Si MAS-NMR and showed that a geopolymer matrix was formed. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) imaging showed the interaction of the fly ash with the geopolymer, which was related to the leachate data and also the maximum percentage fly ash addition.     

Pure, single phase, high crystalline, chamfered-edge zeolite 4A synthesized from coal fly ash for use as a builder in detergents

Single phase chamfered-edge zeolite 4A samples in pure form with a high crystallinity were synthesized by applying step-change of synthesis temperature during hydrothermal treatment of coal fly ash. The calcium binding capacity of these zeolite 4A samples (prepared from coal fly ash) and the commercial detergent grade zeolite 4A were tested for usage as a detergent builder. The results show that these zeolite 4A samples behaved similarly as the commercial one in removing calcium ions during the washing cycle. Moreover, from the leaching tests (evaluation of toxicological safety), the results show that these zeolite 4A samples leached the same elements (Sb, As, Se and Tl) as the commercial one with the concentrations in the same order of magnitude. This shows that the toxicological effect of the coal fly ash converted zeolite 4A was not worse than that of the commercial sample. Finally, economic and environmental aspects of converting coal fly ash to useful products were discussed.     

粉煤灰提取白炭黑和氧化铝的研究

粉煤灰是我国当前排量最大的工业废渣之一,年排渣量已达3亿t以上,大量堆积的粉煤灰会对自然生态环境造成严重的危害。综合利用粉煤灰,实现粉煤灰的资源化利用,对于治理粉煤灰的污染具有十分重要的意义。文章提出先采用碱液常压浸出粉煤灰,生产白炭黑,然后采用碱石灰烧结法生产氧化铝,可实现粉煤灰的经济综合利用。研究表明：用苛性碱液在常压（＜125 ℃）下浸取粉煤灰45 min,粉煤灰中硅的提取率达到72.5 %以上,而氧化铝的总溶出率＜1.2 %;碳分浸取得到的硅酸钠溶液,可以生产氧化硅含量＞99 %的优质白炭黑,溶液中氧化硅转化率＞98 %;浸取硅后的渣中氧化铝含量＞55 %,氧化硅含量＜20 %,铝硅比≥2.7,适宜采用碱石灰烧结法生产氧化铝。碱石灰烧结法适宜的配方为：碱比 0.95～1.0,钙比 1.8～2.0;烧结温度宜为1 200～1 250 ℃;熟料溶出温度75～85 ℃,时间10～20 min,氧化铝回收率＞86 %。综合利用粉煤灰生产白炭黑和氧化铝,经济效益和社会效益显著。     

ENCAPSULATION OF TOXIC WASTE MATERIALS BY FLY ASH AGGLOMERATION

A major shift to coal as a fuel source has resulted in the generation of vast quantities of difficult to dispose of coal residues. Innovative utilization of such coal combustion by products is essential A procedure has been developed by which by-products from Iowa Power stations can be agglomerated into inert pellets of high compressive strength. Evaluation of the leachate potential of such materials showed heavy metal concentrations to be well below the allowable limits of the EPA toxicity tests. The commercial utilization potential as artificial aggregates is very high

This paper focuses on the feasibility of using the cementing properties and agglomeration characteristics of such coal conversion by-products to encapsulate and immobilize hazardous waste materials. Sludges from the electroplating industries were encapsulated in a fly ash matrix. Encapsulation is a novel approach to treating toxic wastes and combines the principles of stabilization/ solidification and agglomeration in containing the pollutants. The agglomerates were subjected to the EPA leaching test, x-ray diffraction analysis, and SEM/ EDXA. Compressive strengths of the agglomerates were also determined

Initial results indicate that encapsulation of sludges in such a matrix stabilizes the toxic and metallic elements in an insoluble form by encasement in a low porosity, solid matrix so mat significant leaching does not occur     

Explosibility boundaries for fly ash/pulverized fuel mixtures

Incomplete combustion and subsequent fuel contamination of a waste stream can pose a serious explosion hazard. An example of this type of incident is the contamination of fly ash with unburned pulverized coal. The coal, if present in sufficient quantities in the mixture, can act as a fuel source for a potential explosion. Experiments were conducted in a 20l Siwek explosibility test chamber to determine the minimum fuel contamination of fly ash required to form an explosible mixture. A sample of fly ash from Ontario Power Generation (OPG) (Ont., Canada) was artificially contaminated with Pittsburgh pulverized coal dust (the surrogate used to represent unburned fuel dust). Additionally, the influence of fly ash particle size on the amount of fuel contaminant required to form an explosible mixture was examined. Fine and coarse size fractions of fly ash were obtained by screening the original sample of OPG fly ash.The results show that at least 21% Pittsburgh pulverized coal (or 10% volatile matter) was required to form an explosible mixture of the original fly ash sample and coal dust. The results also illustrate that fly ash particle size is important when examining the explosibility of the mixture. The fine size fraction of fly ash required a minimum of 25% coal dust (12% volatile matter) in the mixture for explosibility, whereas the coarse fly ash required only 10% coal dust (7% volatile matter). Thus, the larger the particle size of the inert fly ash component in the mixture, the greater the hazard.     

Investigation of reactions in high-alumina fly ash and lime pastes

By-product fly ash from coal combustion generally contains a high percentage of active silica and smaller amounts of alumina, although some coals can have higher alumina contents (30 to 40%). During our experimental tests on the utilization f fly ash in road and highway foundation sheets, we have found a fly ash poor in silica, having an exceptionally high alumina content. This material has shown a good reactivity towards lime paste, giving hardened mixtures with high mechanical properties.     

Arsenic and lead release from fly ash stabilized/solidified soils under modified semi-dynamic leaching conditions

A fly ash-based stabilization/solidification (S/S) technique was investigated using field soil samples contaminated with arsenic (As) and lead (Pb). A semi-dynamic leaching test was used to evaluate the effectiveness of the S/S treatment. By assessing the cumulative fractions of leached As and Pb, the effective diffusion coefficient (D(e)) and a leachability index (LX) were measured and used for evaluating the effectiveness of the S/S treatment. Overall, As release was reduced by 98.3% and Pb release was reduced by 98.5% upon addition of 25% Class C fly ash. The mean D(e) decreased significantly and the mean LX was always above 9 for all treated samples, indicating that the treated soils were acceptable for "controlled utilization". The mechanism controlling As leaching from all treated samples appeared to be a mixture of wash-off and diffusion. Diffusive As release was proportional to fly ash content. The mechanism controlling Pb leaching when samples were treated with 25% fly ash appeared to be wash-off.     

A study on the chemical and mineralogical characterization of MSWI fly ash using a sequential extraction procedure

The presence of heavy metals in municipal solid waste incineration (MSWI) fly ash is of environmental concern due to their leaching potential in landfill environments. Sequential chemical extraction was performed on fly ash samples from a large-scale municipal solid waste incineration plant in East China. The transformation of the mineralogical species of fly ash during the sequential extraction was studied using X-ray fluorescence (XRF) and X-ray powder diffraction (XRD). The leaching behavior of heavy metals such as zinc, lead, cadmium and copper in MSWI fly ash was considered to have a dependency relationship with the components of calcium, such as aphthitalite, calcite, anhydrite and calcium aluminate or calcium aluminosilicate.     

Utilization of coal fly ash in the glass-ceramic production

Manufacturing the glass-ceramic has been proposed as a useful choice to recycle coal fly ash from power plants. In this work, a glass-ceramic of SiO2-Al2O3-Fe2O3-CaO family was synthesized by mixing 90 wt% of coal fly ash, from a power plant in west of China, with Na2O, and then melted at 1350 degrees C. The ceramization of the obtained glass was carried out at 770 degrees C for 2h. Esseneite and nepheline were found present as major crystal phases. The produced glass-ceramic exhibited good chemical durability as well as good mechanical properties. The toxicity characteristic leaching procedure (TCLP) method found that the glass-ceramic was non-hazardous.     

Leaching behavior of heavy metals from municipal solid wastes incineration (MSWI) fly ash used in concrete

The characteristics of municipal solid waste incineration (MSWI) fly ash, surface leaching toxicity and successive leaching concentration of heavy metals from MSWI fly ash-cement hardened pastes were studied. And, the relationships between leaching concentrations of heavy metals and leaching time were also discussed. Experimental results showed that immobilization effect of cement on MSWI fly ash is good. Even if MSWI fly ash-cement hardened pastes were damaged, the leaching toxicity is still in a safety range. In early leaching stage, the surface leaching rate is relatively a little high, up to 10(-5)-10(-4)cmd(-1) order of magnitude, in the later time of leaching, its rate rapidly declined, down to 10(-7). Most of leached heavy metals are produced at early ages. The leaching concentration of heavy metals and leaching time has strong positive relationships. In factual utilizing circumstances, heavy metals' leaching from MSWI fly ash-cement hardened pastes is a very slow and gradually diluting process. The leaching toxicity of heavy metals is far lower than that of the National Standard of China, and minimum harmful matters can be contained and released in the environment. Reusing of MSWI fly ash as partial replacement for cement in concrete mixes is potentially feasible.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Effective use of fly ash slurry as fill material

A lot of effort has been put into increasing coal ash utilization; however, 50% of total amount is disposed of on land and in the sea. Several attempts have been reported recently concerning slurried coal fly ash use for civil engineering materials, such as for structural fill and backfill. The authors have studied this issue for more than 15 years and reported its potential for (1) underwater fills, (2) light weight backfills, and (3) light weight structural fills, through both laboratory tests and construction works. This paper is an overview of the results obtained for slurry, focusing on the following. (1) Coal fly ash reclaimed by slurry placement shows lower compressibility, higher ground density, and higher strength than by the other methods. This higher strength increases stability against liquefaction during earthquake. (2) Higher stability of the fly ash ground formed by slurry placement is caused by higher density and its self-hardening property. (3) Stability of fly ash reclaimed ground can be increased by increasing density and also by strength enhancement by cement addition. (4) Technical data obtained through a man-made island construction project shows the advantages of fly ash slurry in terms of mechanical properties such as higher stability against sliding failure, sufficient ground strength, and also in terms of cost saving. (5) Concentration in leachates from the placed slurry is lower than the Japanese environmental law. (6) In order to enlarge the fly ash slurry application toward a lightweight fill, mixtures of air foam, cement and fly ash were examined. Test results shows sufficient durability of this material against creep failure. This material was then used as lightweight structural fill around a high-rise building, and showed sufficient quality. From the above data, it can be concluded that coal fly ash slurry can be effectively utilized in civil engineering projects.     

Environmental behavior of cement-based stabilized foundry sludge products incorporating additives

A series of experiments were conducted to stabilize the inorganic and organic pollutants in a foundry sludge from a cast iron activity using Portland cement as binder and three different types of additives, organophilic bentonite, lime and coal fly ash. Ecotoxicological and chemical behavior of stabilized mixes of foundry sludge were analyzed to assess the feasibility to immobilize both types of contaminants, all determined on the basis of compliance leaching tests. The incorporation of lime reduces the ecotoxicity of stabilized mixes and enhances stabilization of organic pollutants obtaining better results when a 50% of cement is replaced by lime. However, the alkalinity of lime increases slightly the leached zinc up to concentrations above the limit set under neutral conditions by the European regulations. The addition of organophilic bentonite and coal fly ash can immobilize the phenolic compounds but are inefficient to reduce the ecotoxicity and mobility of zinc of final products.     

垃圾焚烧炉渣-粉煤灰复合水泥的性能研究

研究了垃圾焚烧炉渣及粉煤灰单掺和复掺时硬化水泥浆体的力学性能和水化机理,比较了两者的活性,探讨了两者作为辅助性胶凝材料利用的可行性.研究表明:掺有垃圾焚烧炉渣及粉煤友的复合水泥,其强度均有不同程度的下降,它们的掺入在一定程度上延缓了水泥的水化过程,且垃圾焚烧炉渣的水化反应活性稍高于粉煤灰;掺垃圾焚烧炉渣及粉煤灰的复合水泥中重金属离子浸出量小,在等掺20%的条件下,浸出量远低于国家标准,说明在一定的情况下,焚烧炉渣及粉煤灰作为辅助性胶凝材料使用是安全的.     

Sintering of MSWI fly ash by microwave energy

This study presents the sintering of municipal solid waste incineration (MSWI) fly ash assisted by microwave energy. The composition of fly ash was investigated by chemical sequential extraction and modified microwave digestion method. Effects of process time, container materials, aging time and salt contents were also discussed. The major elements of fly ash are Ca, Cl, Na, Si, K, Al, Mg, and Zn, and the metal species, Zn, Cr, Pb, Ca, and Cu, are mainly in the oxide phase. Under microwave processing, the fly ash was sintered into a glass-ceramics and the leaching concentrations of heavy metals were restrained. The stabilization efficiency increased with an increase in processing time in most of the cases. Better stabilization efficiency of fly ash was discovered by using the SiO(2) or Al(2)O(3) container than by using the graphite plate/SiC plate. The presence of salt in the fly ash could enhance the sintering and stabilization of fly ash. During the aging time of 0-30 days, negligible Pb in the sintered fly ash was leached out, and the leaching concentration was lower than the criterion.     

工业固体废弃物资源综合利用技术现状

工业固废的综合利用已经成为建设资源节约型、环境友好型社会的重要措施。详细介绍了近几年来我国工业固废产生和处理的总体情况;概括与总结了粉煤灰、炉渣、尾矿、副产石膏、赤泥以及煤矸石等几种总产生量较大、品种较为集中的大宗工业固废的利用现状;同时以煤矸石为例详细介绍了其综合利用概况以及产业化情况,特别是利用其制备高性能混凝土、新型耐火材料、新型功能材料等高值产品将是未来的重要发展方向;最后,展望了我国大宗工业固废资源化利用技术的发展趋势。     

Solidification/stabilization of electric arc furnace dust using coal fly ash. Analysis of the stabilization process

In this paper, the stabilization of electric arc furnace (EAF) dust containing hazardous metals such as Pb, Cd, Cr or Zn is described. The treatment involves a waste solidification/stabilization (S/S) process, using coal fly ash as the fundamental raw material and main binder. The article also contains a brief review of the most important recent publications related to the use of fly ash as S/S agents.The efficacy of the process has been evaluated mainly through leaching tests on the solidified products and compliance with some imposed leachate limits. The concentration of metals leaching from the S/S products was strongly leachate pH dependent; thus, the final pH of the leachate is the most important variable in reaching the limits and, therefore, in meeting the stabilization goals.In this study, the dependence relationship between the leachate pH and the concentrations of metals in the leachate are analyzed; in some cases, this allows us to estimate the speciation of contaminants in the S/S solids and to understand the mechanism responsible for reduced leachability of heavy metals from solidified wastes.     

Anomalous transient leaching behavior of metals solidified/stabilized by pozzolanic fly ash

This study presents observations on the transient leaching behavior of chromium, cadmium, and aluminum that were solidified/stabilized by pozzolanic fly ash. These three metals were selected since they were present in a simulated waste stream generated by an evaporator during plutonium purification and also because the minimum solubility of these metals occurs at significantly different pHs. The transient pH behavior of the toxicity characteristic leaching procedure (TCLP) leachate showed a monotonic increase for all cases, but the equilibrium value was affected by process conditions. The transient leachate concentration behavior showed curves with one or two local maxima for some cases and curves with a monotonic increase for other cases. Data from the leaching experiments was compared to the solubility curves for the hydroxides of each metal since it was assumed that the highly alkaline conditions inside the fly ash waste would cause the metals to precipitate as hydroxides after initially dissolving in the acidic leaching solution. It was found that of the three metals, only cadmium followed the solubility curve for pure hydroxide solutions or for fly ash systems currently reported in the literature.