SEM–EDS characterization of inorganic material in refuse-derived fuels

The utilisation of refuse-derived fuel (RDF) in energy production is restricted by their inorganic impurities, such as heavy metals and chlorine. In this contribution, three different types of RDF were studied by SEM–EDS. These materials originated from three locations: construction sites, households, and supermarkets. Several fuel samples of every type of RDF were used in this study. The compositional distributions of the inorganic particles were determined directly from each fuel and the results are presented as quasiternary diagrams. The presentation method makes it possible to identify inorganic particles such as sand, alkali metal chlorides, calcium chloride, gypsum, lime, titanium pigment, iron as an element or oxide, and metallic aluminium from fuel. The results can be used to discuss the origin of different inorganic components in these materials and serve as a base for discussion of the suitability to use each waste material as fuel. It also facilitates the design of appropriate purification steps that are needed.     

Heat of hydration of Portland Cement–Metakaolin–Fly ash (PC–MK–PFA) blends

In the present study two pozzolanic materials are used, Metakaolin (MK) and Fly Ash (PFA), as binary and ternary partial replacement binders with Portland cement (PC) to investigate their effect on the rate of heat evolution (dQ/dt in J/gh) during hydration, and the heat of hydration, (Q(t) in J/g). For binary PC–PFA blends PC hydration is enhanced in the very early stages of hydration, but at extended periods (up to 120 h) an increase in PFA replacement level causes a systematic reduction in heat output. For binary PC–MK blends the results suggest that the MK initially diminishes PC hydration but the subsequent pozzolanic reaction of MK increasingly contributes to the heat output causing some blends to exceed the heat output of the PC control. For both systems a principal controlling factor in the PC hydration rate (and the heat evolution rate) is the water requirement of the pozzolan, but for PC–MK blends the pozzolanic reaction of the MK makes a significant contribution to the heat output. However this reaction is controlled both by the availability of water and the supply of Ca²⁺ ions from the hydrating PC which introduces an increasing level of complexity to the heat output versus time profiles. When combining MK and PFA in ternary PC–MK–PFA blends the MK has a dominant influence on the heat output versus time profiles.     

Fly ash effects: I. The morphological effect of fly ash

The morphological effect is an important part of fly ash effects. The paper analyzes emphatically this effect and points out that it is composed of the filling role, surface role and lubricating role. For different fly ash, these roles are different. They must be considered synthetically when the morphological effect is analyzed. Analyzing result shows that the filling role is relative to the particle size, the surface role is relative to the specific surface area and the water affinity and the lubricating role is relative to the shape of particle. The morphological effect of fly ash is the synthetical embodiment of these roles.     

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.     

Characteristics of coal combustion products (CCP's) from Kentucky power plants, with emphasis on mercury content

The Center for Applied Energy Research conducts a survey of Kentucky's coal-fired power plants every five years. The last survey was conducted in 2002 and covered most units at all of the plants in Kentucky. Special emphasis was placed on the spatial distribution of ash products, with each row of ESP's or baghouses samples wherever possible. In this manner, we can track the change in concentration of trace elements with relative temperature of the flue gas. Certain elements, such as Zn, Pb, and As, are known to be temperature dependent. The behavior of Hg, while also temperature dependent, is more complex owing to the adsorption of Hg on fly ash carbon. The survey provides a wide array of coal sources, ESP/baghouse collection temperatures, and fly ash carbon composition, all important in determining the behavior of Hg in the flue gas. In addition, many plants have FGD systems, allowing an assessment of the efficiency of FGD in capturing Hg from the post-ESP flue gas.     

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.     

神华宁煤煤化工基地粉煤灰的资源化利用

简述了煤化工生产过程中产生的粉煤灰来源,通过XRD、SEM、FT-IR等手段对气化炉粉煤灰和锅炉粉煤灰的性质迚行检测,根据分析检测结果,提出了煤化工粉煤灰资源化综合利用的建议。选用适宜的粉煤灰处理技术,创建煤化工基地粉煤灰综合处理示范项目,对基地粉煤灰利用乃至全国煤化工行业粉煤灰能源化利用都有重要的意义和积极的推动作用。     

粉煤灰电石渣在农村公路建设中的应用

研究了以粉煤灰、电石渣、水泥为主要胶凝材料的混凝土性能：通过实验室及实际工程研究和应用,表明当粉煤灰：电石渣比例为3：1,并掺入适量激发剂和水泥的情况下。其性能可满足农村低交通量公路行车要求,并且具有显著的经济性。     

The Silicate/non-silicate distribution of metals in fly ash and its effect on solubility

In a study at DOE's National Energy Technology Laboratory, 32 Class F fly ash samples from pulverized coal (PC) power plants were dissolved in concentrated nitric acid and in hydrofluoric acid to estimate the distribution of metals in non-silicate and silicate matrices. Nineteen cations occurred to some extent in both phases. Using a column leaching method, the release of the metals was determined with four leachant solutions; the pH of the leachants ranged between 1.2 and 12. Although the amount of an element extracted from the fly ash was low, solubility in alkaline leachants was correlated with elements in non-silicate compounds. Solubility in acid solutions was correlated more strongly with silicate phase concentration.     

Speciation of major and selected trace elements in IGCC fly ash

The speciation of Ga, Ge, Ni, V, S and Fe in fly ash from IGCC power plant were investigated for possible further extraction process by combining conventional mineral and chemical analysis, leaching tests, wet sequential extraction, Mössbauer and XAFS spectroscopies. The results shown that Ge occurs mainly as water-soluble species, GeS and/or GeS₂ and hexagonal GeO₂. Ga is present as an oxide, Ni occurs mainly as nickeline (NiAs), with minor proportions of Ni arsenates and vanadium as V(III) with minor amounts of V(IV) in the aluminosilicate glass matrix. Pyrrhotite and wurtzite-sphalerite are sulfide species containing Fe and Zn, but an important fraction of iron is also present in the aluminosilicate glass. These clear differences between the speciation of the above elements in this material and those reported for fly ash from conventional PC combustion.     

Comparison of chars in slag and fly ash as formed in pf boilers from B?dzin Power Station (Poland)

The amount of unburned organic matter in solid residues from coal combustion process is one of the indicators of the process and may influence their usage as by products. During the examination of slag and fly ash from B?dzin Power Station (Poland) the following forms of unburned coal were distinguished: crassispheres, tenuispheres, isotropic and anisotropic networks, tenuinetworks, honeycombs, inertinite and detritus. Slag characterises higher crassispheres and networks contents while high detritus contents are typical of fly ash. Spheres content in both slag and fly ash is always lower than vitrinite content in the feed coal. Fusinite content in the feed coal is lower than inertinite content in the solid residues. Other inertinite macerals probably participated in the formation of honeycombs.     

A comparison of white rice husk ash and silica as fillers in ethylene–propylene–diene terpolymer vulcanizates

White rice husk ash (WRHA) and silica filled ethylene–propylene–diene terpolymer (EPDM) vulcanizates were prepared using a laboratory size two‐roll mill. Curing characteristics and physical properties of vulcanizates were studied with respect to the filler loading and filler type. Filler loading was varied from 0–50 parts per hundred resin (phr) at 10 phr intervals. Curing was carried out using a semi‐efficient vulcanization system in a Monsanto rheometer. Enhancement of the curing rate was observed with increasing WRHA loading, whereas the opposite trend was observed for silica‐filled vulcanizates. It was also indicated by the maximum torque and Mooney viscosity results that WRHA offers processing advantages over silica. Compared to the silica‐filled vulcanizates, the effect of filler loading on the physical properties of WRHA‐filled vulcanizates was not significant. According to these observations, WRHA could be used as a diluent filler for EPDM rubber, while silica can be used as a reinforcing filler. © 2001 Society of Chemical Industry     

Thermal stability of mercury captured by ash

The thermal stability of mercury captured by ash was studied by sampling ash throughout the collection train of two Kentucky power plants. Sampling occurred over multiple years and involved both fresh and archived samples. During one ash collection episode, sampling was from the combustion of a single pulverized coal feed. The other collections involved ash from blended feeds. Ash was collected from economizer, mechanical and electrostatic precipitator hoppers. Feed coals, rejects and bottom ash were also sampled. Fractions of all the samples were heated in a thermal analyzer to maximum temperatures increased sequentially from 100 to 500 °C in 100 °C increments. The mercury content of the spent material was then determined by analysis of the solids for Hg. From this data the thermal decomposition temperature of the captured mercury was determined. The total mercury captured by each sample, thermal stability of the mercury in relation to collection site, and correlations between mercury capture and chemical composition of the sample were also determined. The data showed that mercury was released between 300–400 °C for all ash samples. The thermal release of Hg between 300–400 °C was studied in greater detail by following the Hg release in several samples at 25 °C intervals from 300–400 °C. The concentration of mercury captured in the ESPs hoppers was greater than in the ash collected from the economizer or mechanical separators.     

Fly ash and coal char reactivity from Thermo-gravimetric (TGA) experiments

The purpose of this research is to determine the reactivity of a sample of high carbon fly ash obtained from a circulating fluidized bed (CFB) gasification system and benchmark it against three other chars prepared at different pyrolysis temperatures in a laboratory drop tube furnace (DTF).Isothermal and non-isothermal thermo-gravimetric (TGA) experiments were used to determine sample reactivities. Structural analysis tests were carried out to establish the influence of the pore characteristics and Scanning Electron Microscope (SEM) pictures were taken for sample morphology. In-spite of high (BET) surface area and pore volume; reactivity parameters such as activation energy, kinetic rate coefficient, half life, burnout temperature and time proved the fly ash to be the least reactive. The low reactivity is associated with its carbon thermal deactivation. Non-isothermal tests also show the fly ash to be heterogeneous in composition. Of all the samples, the char prepared in the laboratory at the lowest pyrolysis temperature was the most reactive.     

Environmental chamber measurements of mercury flux from coal utilization by-products

An environmental chamber was constructed to measure the mercury flux from coal utilization by-product (CUB) samples. Samples of fly ash, FGD gypsum, and wallboard made from FGD gypsum were tested under both dark and illuminated conditions with or without the addition of water to the sample. Mercury releases varied widely, with 7-day experiment averages ranging from −6.8 to 73 ng/m² h for the fly ash samples and −5.2 to 335 ng/m² h for the FGD/wallboard samples. Initial mercury content, fly ash type, and light exposure had no observable consistent effects on the mercury flux. For the fly ash samples, the effect of a mercury control technology was to decrease the emission. For three of the four pairs of FGD gypsum and wallboard samples, the wallboard sample released less (or absorbed more) mercury than the gypsum.     

Leaching characteristics of selected Korean fly ashes and its implications for the groundwater composition near the ash disposal mound

Currently only 20% of the fly ash produced in Korea is utilised for industry, and the remainder is disposed as waste in landfill sites. Both anthracite and sub-bituminous coals are burnt in Korea. Fly ash and coal samples were collected from five different coal-fired power stations in Korea and analysed for their chemistry and mineralogy. Batch leaching tests were also carried out to investigate the leaching behaviour of selected fly ashes. The fly ash leachate chemistry was compared with the groundwater taken directly from the monitoring well installed in one of the power stations. The anthracite coals contain illite, pyrophyllite and kaolinite whereas kaolinite is the representative clay mineral for the sub-bituminous coals. Anthracite coals were higher in Si, Al and K than the sub-bituminous coals, reflecting higher mineral matter contents in the anthracite coals. Mullite and quartz are the main mineral phases for two different types of the fly ashes, with some iron oxides. The chemical compositions of the anthracite and sub-bituminous fly ashes are comparable with each other, except for extraordinary high concentrations of Cr for one anthracite fly ash. Most of the trace elements in the ash were enriched in the finer fraction, indicating surface associations. Although, some elements including Na, K, Ca and Cu were released rapidly in the initial stage of leaching, measurable amounts of metals were still detectable in the fly ash leachate treated several times with distilled water. Such leaching behaviour indicates slow and long-term leaching of elements associated with the glass fractions of the ash particle. This was confirmed by leaching of weathered fly ash, which had been disposed of for several years. Comparison of the ash leachate, treated with 0.1N-HCl, fly ash slurry in the ash pond and the groundwater indicate the influence of the ash leachate from the ash disposal mound on the groundwater composition.     

Synthesis and characterization of novel solid base catalyst from fly ash

A new type of solid base catalyst was synthesized by chemical and thermal activation of fly ash, collected from Thermal Super Power Station situated in Kota, Rajasthan, India. The chemical activation was carried out by 50 wt.% NaOH followed by thermal activation at 450 °C. The modified physiochemical property of solid base fly ash (SBFA) was determined by X-ray diffraction, FT-IR spectroscopy, Scanning Electron Microscopy, N₂ adsorption-desorption studies and Flame Atomic Absorption Spectrophotometry. The results reveal that the catalyst is nano-crystalline in nature with crystallite size 11 nm and particle size in the range 840 nm to 6.95 μm. The surface basicity and therefore, catalytic activity in SBFA was originated by increased hydroxyl content as compared to fly ash, suggesting that the catalyst possess higher surface active sites. The basicity of the catalyst was measured by liquid phase, solvent free, single step condensation of benzaldehyde with cyclohexanone giving higher conversion (>70%) and selectivity (>80%) of desired product α,α′-dibenzylidenecyclohexanone. This excellent conversion shows that the catalyst has sufficient basic sites both on the surface and in the bulk, responsible for the catalytic activity. Furthermore, this catalyst may replace conventional environmentally hazardous homogeneous liquid bases making an ecofriendly; solvent free, solid base catalyzed process. The application of fly ash to synthesize a solid base catalyst finds a noble way to utilize this abundant waste material.     

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).     

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.     

Production of ethanol by continuous fermentation and liquid–liquid extraction

A continuous pilot plant was constructed for fermentation production of ethanol, using liquid–liquid extraction to remove the product and with recycle of the fermented broth raffinate. The plant was operated for up to 18 days with feed glucose concentrations in the range 10·0–45·8% (w/w). The solvent was n-dodecanol and immobilised yeast was used to overcome the problem of emulsification. The concentration of by-products in the fermented broth had no adverse effect on the rate of ethanol production. A mathematical model to predict the time required for achievement of 99% of the steady-state by-products concentrations was shown to be in good agreement with the experimentally determined concentration of the main by-product, glycerol. At a feed glucose concentration of 45·8% (w/w), the aqueous purge was equivalent to 2·8 m³ of effluent per m³ of ethanol produced and represented a 78% reduction in the volume of the aqueous purge compared with using a feed containing 10% (w/w) glucose.