Preparation and characterization of fully waste-based glass-ceramics from incineration fly ash,waste glass and coal fly ash

Municipal solid waste incineration (MSWI) fly ash (FA) is a typical hazardous waste due to its high contents of toxic heavy metals, and hence its disposal has attracted global concern. In this work, it was recycled into environmental-friendly CaO–Al₂O₃–SiO₂ system glass-ceramics via adding coal fly ash (CFA) and waste glass (WG). The effects of CaO/SiO₂ ratios and sintering temperatures on the crystalline phases, morphologies, mechanical and chemical properties, heavy metals leaching and potential ecological risks of glass-ceramics were investigated. The results showed that wollastonite (CaSiO₃), anorthite (CaAl₂Si₂O₈) and gehlenite (Ca₂Al₂SiO₇) were the dominant crystals in the glass-ceramics, which were not affected by CaO/SiO₂ ratio and sintering temperature. The compressive strength increased, while the Vickers hardness and microhardness decreased as increasing the sintering temperatures from 850 to 1050 °C, which reached their maximum values of 660.69 MPa, 6.14 GPa, and 7.43 GPa, respectively. However, the increase of CaO/SiO₂ ratio resulted into the reduction of the three mechanical parameters. As varying CaO/SiO₂ ratio from 0.48 to 0.86, the maximum compressive strength, Vickers hardness and microhardness were 611.80 MPa, 5.43 GPa, and 6.56 GPa, respectively. Besides, all the glass-ceramics exhibited high alkali resistance of >97%. The extremely low heavy metals leaching concentrations and low potential ecological risk of glass-ceramics further revealed its environmentally friendly property and potential application feasibility.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript>-coated coal fly ash for photocatalyst

In order to more easily separate TiO₂ photocatalyst from treated wastewater, TiO₂ photocatalyst is immobilized on coal fly ash by precipitation method. The titanium hydroxide precipitated on coal fly ash by neutralization of titanium chloride is transformed into titanium dioxide by heat treatment in the temperature range of 300–700 ‡C. The crystalline structure of the titanium dioxide shows anatase type in all ranges of heat treatment temperature. The crystal size of anatase increases with increasing heat treatment temperature, with the drawback being the lower removal ability of NO gas. When the coal fly ash coated with 10 wt% of TiO₂ was calcined at 300 and 400 ‡C for 2 hrs, the average crystal size of anatase appeared about 9 nm, and the removal rates of NO gas were 63 and 67.5%, respectively. The major iron oxide, existing in coal fly ash as impurity, is magnetite (Fe₃O₄). Phase transformation of magnetite into hematite (Fe₂O₃) by heat treatment improves the removal rate of NO gas for TiO₂-coated coal fly ash.     

A new methodology for removal of boron from water by coal and fly ash

High levels of boron concentrations in water present a serious problem for domestic and agriculture utilizations.The recent EU drinking water directive defines an upper limit of 1 mgB/l. In addition, most crops are sensitive to boron levels >0.75 mg/1 in irrigation water. The boron problem is magnified by the partial (∼60%) removal of boron in reverse osmosis (RO) desalination due to the poor ionization of boric acid and the accumulation of boron in domestic sewage effluents. Moreover, high levels of boron are found in regional groundwater in some Mediterranean countries, which requires special treatment in order to meet the EU drinking water regulations. Previous attempts to remove boron employed boron-specific ion-exchange resin and several cycles of RO desalination under high pH conditions. Here, we present an alternative methodology for boron removal by using coal and fly ash as adsorbents. We conducted various column and batch experiments that explored the efficiency of boron removal from seawater and desalinated seawater using several types of coal and fly ash materials under controlled conditions (pH, liquid/solid ratio, time of reaction, pre-treatment, regeneration). We examined the effect of these factors on the boron removal capacity and the overall chemical composition of the residual seawater. The results show that the selected coal and fly ash materials are very effective in removing boron such that the rejection ratio of boron can reach 95% of the initial boron content under certain optimal conditions (e.g., pH = 9, L/S = , reaction time > 6 h). Our experiments demonstrated that use of glycerin enables regeneration of boron uptake into coal, but the boron uptake capacity of fly ash reduces after several cycles of treatment-reaction. The boron removal is associated with Mg depletion and Ca enrichment in the residual seawater and conversely with relative Mg enrichment and Ca depletion in the residual fly ash We propose that the reaction of Ca-rich fly ash with Mg-rich seawater causes co-precipitation of magnesium hydroxide in which boron is co-precipitated. The new methodology might provide an alternative technique for boron removal in areas where coal and fly ash are abundant.     

Ge extraction from gasification fly ash

Water-soluble germanium species (GeS₂, GeS and hexagonal-GeO₂) are generated during coal gasification and retained in fly ash. This fact together with the high market value of this element and the relatively high contents in the fly ashes of the Puertollano Integrated Gasification in Combined Cycle (IGCC) plant directed our research towards the development of an extraction process for this element. Major objectives of this research was to find a low cost and environmentally suitable process. Several water based extraction tests were carried out using different Puertollano IGCC fly ash samples, under different temperatures, water/fly ash ratios, and extraction times. High Ge extraction yields (up to 84%) were obtained at room temperature (25 °C) but also high proportions of other trace elements (impurities) were simultaneously extracted. Increasing the extraction temperature to 50, 90 and 150 °C, Ge extraction yields were kept at similar levels, while reducing the content of impurities, the water/fly ash ratio and extraction time. The experimental data point out the influence of chloride, calcium and sulphide dissolutions on the Ge extraction.     

Preparation of low melting temperature glass-ceramics from municipal waste incineration fly ash

Glass-ceramics have been prepared from air pollution control residues (fly ash) of a municipal solid waste incineration (MSWI) plant in southern China. The use of additives was investigated in order to decrease the melting temperature of the waste and thus to reduce the costs of production of glass-ceramics from the vitrified waste. Results showed that the melting temperature can be decreased significantly from 1500 to 1200 °C, which was achieved by combining the MSWI fly ash with silica sand powder and a Fe₂O₃-rich and CaO-rich iron slag to form a glass in the SiO₂-CaO-Al₂O₃-Fe₂O₃ quaternary phase system. Sodium carbonate and borax were used as fluxing agents and TiO₂ of chemical grade was added as a nucleation agent. The main crystalline phase in both high and low melting temperature glass-ceramics was found to be diopside (Fe-bearing), and the microstructure exhibited the presence of fine crystals of size in the range 100-200 nm which developed at crystallization temperatures in the range 800-900 °C for 1-2 h. The leaching behaviour of the glass-ceramic materials was tested, and it was found to be lower than that of a cement-stabilized body that was fabricated using the same waste for comparison. The results demonstrate the feasibility of reusing MSWI fly ash for glass-ceramic production at relatively low melting temperature, e.g. in a less energy-intensive process, as a viable approach for tackling the problem of hazardous MSWI residues.     

Particle size effect on the filtration drag of fly ash from a coal power plant

In order to investigate the filtration properties of fly ash from a conventional coal power plant, the filtration drag across the dust cake over an absolute fiberglass filter element was measured. A fluidized bed column was utilized to obtain a well characterized particle stream. The cake resistance coefficient was analyzed by the equation proposed by Endo et al. [1998] in order to observe the effect of particle size and polydispersity. The filtration drag was measured for three kinds of particle stream having the geometric mean particle size of 3.15, 6.07, and 7.83 μm and the geometric standard deviation less than 1.44 in the practical operation conditions for the field applications of face velocity of 0.03–0.06 m/s and area dust load up to 0.2 kg/m². A dust cake of smaller particle size showed larger pressure drop even though the porosity was higher and presented high compressibility according to the face velocity. The particle polydispersity was also a dominant factor affecting the compressibility of the dust cake.     

Thermal expansion of slag and fly ash from coal gasification in IGCC power plant

Integrated gasification in combined cycle (IGCC) is an electrical power generation system which is characterized to be a clean coal technology different than conventional process in combustible treatment. IGCC process gives rise to inorganic solid wastes in the form of vitreous slag and fly ashes with singular thermal properties. The gasification of the fuel takes place at high temperature and pressure in reducing atmosphere. Under that conditions, gases such as H₂, N₂ or CO, which are the main components of the gas mixture in the gasifier, show a high solubility in the melt and during the cooling remain enclosed in the vitreous slag. When these wastes are afterward thermal treated in oxidizing conditions, two phenomena occur. The development of a crystalline phase by devitrification of the glassy matrix and the releasing of the enclosed gas, which starts at temperatures nearly to the softening point. At higher temperatures the bubbles with increasing kinetic energy tend to ascent with difficult through the viscous liquid phase and promotes an expansive reaction, giving rise to a foam glass-ceramic product. This paper has been focused on the study of thermal expansion in slag and fly ash samples from the ELCOGAS IGCC power plant located in Puertollano (Spain).     

Use of municipal solid waste incineration fly ash in concrete

With a view of reducing the quantities to be landfilled, the Solvay Company has been working on the development of a new physicochemical treatment for municipal solid waste incineration (MSWI) fly ashes: the Revasol process. This process allows reducing the soluble fraction, fixing heavy metals and eliminating dioxins. This article reports on the characteristics of a treated ash and on its use in concrete. For the latter point, three characteristics were chosen: the compressive strength and the durability of the hardened concrete and its behavior to leaching. From mechanical and durable points of view, the ash incorporated in the concrete behaves like ordinary sand. The leaching tests carried out on the concrete confirm that the process makes it possible to obtain materials without major risks for the environment. Also, these results as a whole suggest that the use of waste in concrete constitutes a potential means of adding value.     

Conversion of coal fly ash into zeolite and heavy metal removal characteristics of the products

Fly ash obtained from a power generation plant was used for synthesizing zeolite. Zeolites could be readily synthesized from the glassy combustion residues and showed potential for the removal of heavy metal ions. By the use of different temperatures and NaOH concentration, five different zeolites were obtained: Na-P1, faujasite, hydroxy sodalite, analcime, and cancrinite. The synthesized zeolites had greater adsorption capabilities for heavy metals than the original fly ash and natural zeolites. Na-P1 exhibited the highest adsorption capacity with a maximum value of about 1.29 mmole Pb g^-1 and had a strong affinity for Pb²⁺ ion. The metal ion selectivity of Na-P1 was determined as: Pb²⁺> Cu²⁺> Cd²⁺> Zn²⁺, consistent with the decreasing order of the radius of hydrated metal ion. The adsorption isotherm for lead by Na-P1 fitted the Freundlich rather than the Langmuir isotherm.     

日本的粉煤灰综合利用

回顾了近年来日本粉煤灰发生量和利用量的推移情况,总结了日本粉煤灰利用领域和途径,举例介绍了为促进粉煤灰的综合利用,日本政府所实行的若干鼓励政策。旨在对中国的粉煤灰综合利用提供一些参考和借鉴。     

Tribo-electrostatic beneficiation of fly ash for ash utilization

The study was conducted to obtain the scale-up factor and the optimum design criteria for the development of a commercial scale electrostatic separator using a continuous, bench-scale electroseparator composed of two vertical electrode plates and an ejector-tribocharger. Tests of the charge density and separation efficiency to study the removal possibility of unburned carbon from coal fly ash were evaluated under various operating conditions. It was found that the experimental conditions for obtaining the maximum charge density were an air flow rate of 1.75 m³/min and a feed rate of less than 50 kg/hr when operated at lower than 30% relative humidity using a SUS304 ejector tribocharger. Also, the optimum instrument conditions for recovering the clean ash with less than LOI3% at yield over 65% when operated at above experimental conditions were found to be a diffuser slit gap of 4 mm, and a distance between diffuser slit and splitter of 15 cm. Overall, the feed rate per unit electrode surface area was about 0.074 kg/cm2 hr, which can be used as a scale-up factor of the electroseparator. Presented at the Int’/Sym. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Structure and properties of forming adsorbents prepared from different particle sizes of coal fly ash

In this paper, different particle sizes of coal fly ash FA-R (D50=15.75μm), FA-A (D50=3.61μm) and FA-B (D50=1.73μm) were treated with NaOH solution to prepare the forming adsorbents FFA-R, FFA-A and FF...     

原料粒度对粉煤灰成型吸附剂结构和性能的影响(英文)

In this paper, different particle sizes of coal fly ash FA-R (D50=15.75μm), FA-A (D50=3.61μm) and FA-B (D50=1.73μm) were treated with NaOH solution to prepare the forming adsorbents FFA-R, FFA-A and FFA-B. The structure and adsorption properties of the forming adsorbents for methylene blue (MB) from aqueous solu-tion were examined. The results showed that the specific surface areas and adsorption capacities of the forming adsorbent for MB increased with decreasing particle size of raw coal fly ashes. The adsorption kinetic data of MB on FFA-R, FFA-A and FFA-B fitted the second-order kinetic model very wel with the rate constants (k2) of 3.15 × 10?2, 3.84 × 10?2 and 6.27 × 10?2 g·mg?1·min?1, respectively. The adsorption process was not only con-trol ed by intra-particle diffusion. The isotherms of MB on FFA-R, FFA-A and FFA-B can be described by the Lang-muir isotherm and the Freundlich isotherm, and the adsorption processes were spontaneous and exothermic. ? 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. Al rights reserved.     

Mode of occurrence of arsenic in feed coal and its derivative fly ash, Black Warrior Basin, Alabama

An arsenic-rich (As = 55 ppm) bituminous feed coal from the Black Warrior Basin, Alabama and its derivative fly ash (As = 230 ppm) were selected for detailed investigation of arsenic residence and chemical forms. Analytical techniques included microbeam analysis, selective extraction, and As K-edge X-ray absorption fine-structure (XAFS) spectroscopy. Most As in the coal is contained in a generation of As-bearing pyrite (FeS₂) that formed in response to epigenetic introduction of hydrothermal fluids. XAFS results indicate that approximately 50% of the As in the coal sample occurs as the oxidized As(V) species, possibly the result of incipient oxidation of coal and pyrite prior to our analysis. Combustion of pyrite and host coal produced fly ash in which 95% of As is present as As(V). Selective extraction of the fly ash with a carbonate buffer solution (pH = 10) removed 49% of the As. A different extraction with an HCl-NH₂OH mixture, which targets amorphous and poorly crystalline iron oxides, dissolved 79% of the As. XAFS spectroscopy of this highly acidic (pH = 3.0) fly ash indicated that As is associated with some combination of iron oxide, oxyhydroxide, or sulfate. In contrast, a highly alkaline (pH = 12.7) fly ash from Turkey shows most As associated with a phase similar to calcium orthoarsenate (Ca₃(AsO₄)₂). The combined XAFS results indicate that fly ash acidity, which is determined by coal composition and combustion conditions, may serve to predict arsenic speciation in fly ash.     

Parametric optimization of packed bed for activated coal fly ash waste heat recovery using CFD techniques

Coal fly ash is an industrial solid waste generated from coal preparation during the processing and cleaning of coal for electric power generation. Comprehensive investigation on the reutilization of waste heat of activated coal fly ash is of great economic significance. The method of recovering the waste heat, proposed in this study,is the transfer of heat from activated coal fly ash to gas with the movement of air using the packed bed, providing valuable energy sources for preheating the raw coal fly ash to reduce the overall energy consumption. The investigation is carried on the heat transfer characteristics of gas–solid(activated coal fly ash) phases and air temperature fields of the packed bed under some key conditions via computational fluid dynamics. A two dimensional geometry is utilized to represent key parts of packed bed. The distribution mechanism of the temperature field for gas phase is analyzed based on the transient temperature contours at different times. The results show that the obtained rule of gas–solid heat transfer can effectively evaluate the influences of operating parameters on the air temperature in the packed bed. Simultaneously, it is found that no temperature differences exist in the hot air at the outlet of the packed bed. The investigation provides guidance for the design and optimization of other similar energy recovery apparatuses in industries.     

Nano-crystal glass-ceramics obtained from high alumina coal fly ash

Glass has been obtained by melting high alumina coal fly ash with fluxing additives. A thermal treatment was employed to convert the obtained glass into nano-crystal glass-ceramics. X-ray diffraction (XRD) patterns show that the main crystalline phases in both the glass-ceramics are anorthite (CaAl₂Si₂O₈) and wollastonite (CaSiO₃). The crystals are homogeneously dispersed within the parent glass. The average crystal size is below 200 nm. Physical and mechanical properties, such as density, thermal expansion coefficient, hardness, and bending strength, of the glass have been examined and the corresponding microstructures are discussed. The results demonstrate that the glass-ceramics have potential for a wide range of construction application.     

Ceramic tiles derived from coal fly ash: Preparation and mechanical characterization

Coal fly ash (CFA) accounts for a large fraction of the solid waste produced in China. Hence, there is an urgent need for the effective utilization of CFA, for example, as a raw material for ceramics production. In this study, clay- and feldspar-like materials fabricated by alkali activation pre-treatment of CFA were mixed with untreated CFA (regarded as a quartz-like material) and sintered to prepare fully ash-based ceramic tiles. The obtained tiles exhibited excellent sintering properties, e.g., low firing temperature and a wide sintering range; further, they showed better green strength (due to hydrogen bonding) and post-sintering performance (due to fluxing and mullite skeleton effects) than ceramic tiles produced exclusively from untreated CFA. The fully ash-based ceramic tiles sintered at 1100 °C exhibited optimal post-sintering properties (bulk density, 2.5 g/cm³; rupture modulus, 50.1 MPa; and water absorption, 0%). Thus, the proposed method is well suited for preparing a novel kind of ceramic tiles completely derived from CFA, highlighting its importance in the field of fly ash ceramics.     

Production of glass from coal fly ash

The coal fly ash from a Chinese thermal power plant was vitrified after the addition of ∼10 wt% Na₂O. The glass products have suitable viscosity at 1200 °C and displayed a good chemical durability. The heavy metals of Pb, Zn, Cr and Mn were successfully immobilized into the glass as determined by the toxicity characteristic leaching procedure method. Results indicate an interesting potential for the coal fly ash recycling to produce useful materials.     

Hydrothermal synthesis of zeolites from coal fly ash

The fly ash, from the combustion of coal to produce energy and heat, is an industrial waste, in which large accumulations represent a serious environmental threat. To reduce the environmental burden and improve the economic benefits of energy production, the science and industry focus on the transformation of coal combustion byproducts into new functional materials. The fly ash was studied by modern analytical methods. As a result of the hydrothermal reaction, several types of zeolites were synthesised from the fly ash: analcime, faujasite (zeolite X) and gismondine (zeolite P). It was shown that the experimental conditions (temperature, reaction time and alkali concentration) have a significant influence on the type of zeolite and its content in the reaction products. The series of experiments resulted in building approximate crystallisation field of zeolites and other phases as the first stage of the formation of ceramic membrane and other materials.