Instrumental activation analysis of coal and fly ash with thermal and epithermal neutrons

A systematic comparison of thermal and epithermal irradiations in the instrumental activation analysis of coal and fly ash was made. From a total of 44 elements, the epithermal irradiation technique appeared advantageous in 20 cases, namely Ni, Ga, As, Se, Br, Rb, Sr, Zr, Mo, In, Sb, Cs, Ba, Sm, Ho, Hf, Ta, W, Th and U. Data are presented for the National Bureau of Standards’ coal (SRM 1632) and fly ash (SRM 1633).     

Adsorption of indigo carmine from aqueous solution using coal fly ash and zeolite from fly ash

Coal fly ash, a waste generated at the Figueira coal-fired electric power plant located in Brazil, was used to synthesize zeolite by hydrothermal treatment with NaOH solution at 100 °C for 24 h. The fly ash (FA) and this synthesized zeolite (ZM) that was characterized predominantly as hydroxy-sodalite were used as adsorbents for anionic dye indigo carmine from aqueous solutions. The samples were analyzed by instrumental neutron activation analysis (INAA) for the determination of As, Co, Fe, La, Mo, Na, Sb, Sc, Sm, Th, U and Zn. Effects of contact time and initial dye concentration were evaluated in the adsorption processes. The kinetics studies indicated that the adsorption followed the pseudo-second order kinetics and that surface adsorption and intraparticle diffusion were involved in the adsorption mechanism for both the adsorbents. The Langmuir isotherm model provided the best correlation of the experimental data. The maximum adsorption capacity was found to be 1.48 mg L⁻¹ for FA and 1.23 mg L⁻¹ for ZM. Laboratory leaching and solubilization tests conducted to classify this ZM as if was a waste residue according to the Brazilian regulation classified it as a residue non-hazardous and non-inert.     

Instrumental activation analysis of coal and fly ash with thermal and epithermal neutrons and short-lived nuclides

Instrumental neutron activation analysis is applied to the determination of about 25 elements in coals and fly ash by means of nuclides with half-lives of less than 48 h ; thermal and epithermal irradiations are used. The results indicate that epithermal activation is preferable for twelve of the elements (Ga, As, Br, Sr, In, Cs, Ba, La, Sm, Ho, W and U). Data for SRM 1632 (coal) and SRM 1633 (fly ash) compare favorably with the results obtained by other investigators.     

Homogeneity tests and certification analyses of coal fly ash reference materials by instrumental neutron activation analysis

The instrumental neutron activation analysis technique (INAA) was used for homogeneity tests and certification analyses of coal fly ash reference materials ENO, ECH, and EOP prepared at the Institute of Radioecology and Nuclear Techniques (IRANT), Koice, Czechoslovakia. Quantitative estimation of a degree of inhomogeneity was suggested. The relative standard deviations due to inhomogeneity were found to be <1% for macroconstituents and <3% for minor and trace elements for sample weights about 25 mg. The results of determination of the elements Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, In, K, La, Mn, Na, Nd, Ni, Rb, Sb, Sc, Sm, Sr, Ta, Th, Ti, U, V, W, and Zn were compared with the IRANT certified or information values. NBS SRM 1633a Trace Elements in Coal Fly Ash was also analyzed as a control sample and the results for the above elements were compared with the NBS certified, information or literature available values. From these comparisons, inference was made on the quality of the IRANT specified values for the element contents.     

Thermal conductivity of lightweight aggregate based on coal fly ash

The article presents the results of physical and chemical properties of lightweight aggregates (LWA) obtained by the thermal treatments of raw composition based on fly ash, supplied by electric plants from Serbia. The production process of LWA consists of raw material preparation, plastic shaping?Cextrusion, granulation, and thermal treatment at three temperatures: 1100, 1150, and 1200?°C. The final firing temperature (T?=?1150?°C) is chosen based on the mechanical and physical properties of the designed aggregates. The particle-size distribution of the LWAs is unimodal (d????16?mm) while the density value varies from 0.98 to 1.99?g/cm³. The water absorption values are determined by use of two methods: 24?h of soaking in cold water and 5?h of boiling. The thermal conductivity of unbound, fired LWA particles is determined by measuring the amount of axially transferred heat in the stationary state. The obtained value of the LWA thermal conductivity (???=?0.0872?W/mK, T?=?1150?°C) is suitable for the production of structural concrete blocks with improved thermal insulating properties. Because of their high-porosity and -compressive strength values, the designed LWA could be used instead of the conventional aggregates in the production of concrete blocks. Consequently, a real valorization of the waste material such as fly ash in Serbia was established.     

Microcalorimetric study on the influence of temperature on bacterial coaggregation

Binding isotherms and heats of interaction have been determined at 15, 25, and 40 degrees C for a coaggregating and a non-coaggregating oral bacterial pair. Heats of interaction were measured upon three consecutive injections of streptococci into an actinomyces suspension using isothermal titration calorimetry. After each injection, the number of streptococci injected remaining free in suspension was quantified microscopically and the degree of binding between the two bacterial strains was established. The coaggregating pair shows positive cooperative binding. The highest cooperativity, at 25 degrees C, correlates with a strong, macroscopically visible coaggregation. The non-coaggregating pair shows low cooperativity and lacks macroscopically visible coaggregation. Interactions between the coaggregating partners seem to be mainly due to specific, enthalpically saturable and favorable binding sites. Even though the enthalpic part of the interaction is saturated, cooperativity increases with consecutive injections, implying that the coaggregation phenomenon is driven by entropy gain. The change in heat capacity (DeltaC(p)) is positive for the non-coaggregating pair from 15-40 degrees C as well as for the coaggregating pair beyond 25 degrees C. At lower temperatures the coaggregating pair causes a negative DeltaC(p). The decrease in heat capacity together with an increase in entropy is considered to be indicative of hydrophobic interactions playing an important role in the formation of large coaggregates as observed for the coaggregating pair at 25 degrees C.     

Leachability and analytical speciation of antimony in coal fly ash

A new procedure was described with multiwalled carbon nanotubes as solid phase extraction packing material for the trace analysis of nicosulfuron, thifensulfuron and metsulfuron-methyl in water samples. The possible parameters influencing the enrichment were optimized and the optimal conditions were as followed: eluent, sample pH, flow rate and sample volume were acetonitrile containing 1% acetic acid, pH 3, 8 mL min⁻¹ and 500 mL, respectively. Under the optimal chromatographic separation and SPE conditions, the linear range, detection limit (S/N = 3) and precision (R.S.D., n = 6) were 0.04-40 ng mL⁻¹, 6.8 ng L⁻¹ and 2.5% for nicosulfuron, 0.04-40 ng mL⁻¹, 11.2 ng L⁻¹ and 5.4% for thifensulfuron, 0.02-20 ng mL⁻¹, 5.9 ng L⁻¹, 2.1% for metsulfuron-methyl, respectively. The established method was well employed to determine nicosulfuron, thifensulfuron and metsulfuron-methyl in tap water, seawater, reservoir water and well water samples, and satisfactory results were obtained, the spiked recoveries in the range of 87.2-100.7%, 96.5-105.6% and 83.7-111.1% for them each, respectively.     

Rapid slurry analysis of solid coal and fly ash samples

Coal and coal fly ash samples were analyzed as solid slurries. These preliminary experiments used fast sampling STPF procedures which omitted the pyrolysis step and the matrix modifier. The experiments also used an ultrasonic mixing device that automatically stirred the suspension just before the autosampler probe withdrew the aliquot which it would dispense onto the platform. The combination of these techniques made it possible to reduce the analytical time to less than 1 min per sample. Simple aqueous standards were used for calibration. The NIST SRM 1633a Coal Fly Ash was successfully analyzed for As, Pb and Tl, with results for Se in this material that suggested that more work was required to gain confidence in the determination. The SRM 1632a Coal was successfully analyzed for As and Pb. The methods were the same for both materials. A few mg of the dry solid powder was weighed directly into the autosampler cup followed by a weighed amount (about 1.5 ml) of suspending diluent The characteristic mass was calculated from several aliquots of simple aqueous standards and this value was used to calculate the amount of analyte delivered to the furnace. In the work reported here the detection limits for the elements determined were about 0.5–1 μg/g in the solid sample. With further experience these limits may be improved. The precision for replicates of slurries from the same cup varied from 2 to 10% depending upon the amount of solid sample delivered to the furnace.     

配煤对高熔点煤灰熔融特性影响的研究

采用灰熔点较低的襄阳煤和灰熔点较高的晋城无烟煤组成的混合煤样,利用XRF、SEM、DSC、XRD、三元相图等分析方法,探究了襄阳煤对晋城无烟煤煤灰熔融温度的影响。结果表明,配煤能有效降低高熔点煤灰的熔融温度,当襄阳煤的加入量小于24%时,混合煤灰熔融温度显著降低;襄阳煤的加入量在24%-40%时,混合煤灰熔融温度变化平缓且流动温度低于1 400℃。混合煤灰中的成分在1 000-1 200℃发生一系列的化学反应,主要包括SiO_2与Al_2O_3结合产生高熔点物质莫来石以及Fe_2O_3、CaO与莫来石反应转化形成铁尖晶石、钙长石等新物质,由此造成了煤灰熔融温度的变化。基于BP神经网络对实验数据建立预测模型,其预测效果优于前人总结的经验公式,平均准确度高于99%。利用热力学软件HSC 5.0分析了CaO、Fe_2O_3对降低煤灰熔融温度的影响,分析表明,CaO对莫来石的转化作用优于Fe_2O_3。     

Floating cultivation of marine cyanobacteria using coal fly ash

The aim of this study was to develop improved methodologies for bulk culturing of biotechnologically useful marine cyanobacteria in the open ocean. We have investigated the viability of using coal fly ash (CFA) blocks as the support medium in a novel floating culture system for marine microalgae. The marine cyanobacterium Synechococcus sp. NKBG 040607 was found to adhere to floating CFA blocks in liquid culture medium. Maximum density of attached cells of 2.0×10⁸ cells/cm² was achieved using sea water. The marine cyanobacterium Synechococcus sp. NKBG 042902 weaklyadhered to floating CFA blocks in BG-11 medium. Increasing the concentration of calcium ion in the culture medium enhanced adherence to CFA blocks.     

Chemical characterization of density separated submicrometer coal fly ash

A new geometrical particle size separation method in the range of submicrometer has been developed for coal fly ash. Coal fly ash particles prefractionated less than 5m in geometrical diameter were fractionated with a coupling of supersonical dispersion in methyl alcohol and filtration through antistatic Nucleopore filter into >1.0, 1.0–0.8, 0.8–0.6m.Submicrometer (1.0–0.6m) and micrometer coal fly ash (25–20m) were separated into six density fractions and their compositions measured by SEM-EDX were compared. For the both size fractions, for the low density fractions (<2.8 g/cm³) consisted mainly of aluminosilicates and the fractions of 2.8–3.2 g/cm³ consisted of oxides of aluminum, silicon and calcium, and in the fraction above 3.2 g/cm³ iron was rich. In submicrometer fly ash, phosphor and sulfur concentrated to the particles rich in calcium. In the heaviest fraction, the particles containing over 30 wt% titanium as oxide observed among the particles rich in iron. These fractions were revealed not as a single component, but as mixtures of several components.     

A study of the chemical forms or species of manganese found in coal fly ash and soil

The chemical speciation of manganese of environmental and toxicological interest was undertaken in coal fly ash and soil. Hard coal used in combustion creates considerable quantities of waste ash. The greatest quantities of industrial ashes are stored in the form of waste-heaps, which create a serious problem as the source of inorganic pollution. It is necessary to identify physical and chemical properties of ash, especially when analyzing the pollution of soil by trace metals, which are potentially mobile in environment. In this work, a new analytical method has been developed and used successfully for identification and determination of chemical forms of manganese in coal fly ash and soil. The basic chemical forms of metals contained in the environmental samples (fly ash and soil) can be described by using sequential extraction method. To identify Mn ions, the UV-VIS spectrophotometric method was used by means of comparative analysis of spectrophotometric spectra of appropriate Mn ions in the standard solutions and solutions obtained after extraction. The concentration of manganese in all solutions was determined by the Flame Atomic Absorption method. The experimental approach and analytical method developed in this study appear adequate for this purpose and can therefore be used for similar research.     

Microcalorimetric study of protein adsorption onto calcium hydroxyapatites

To clarify the adsorption mechanism of proteins onto calcium hydroxyapatite (Hap), the present study measured adsorption (DeltaHads) and desorption (DeltaHdes) enthalpies of bovine serum albumin (BSA; isoelectric point (iep) 4.7, molecular mass (Ms) 67,200 Da, acidic protein), myoglobin (MGB; iep=7.0, Ms=17,800 Da, neutral protein), and lysozyme (LSZ; iep=11.1, Ms=14,600 Da, basic protein) onto Hap by a flow microcalorimeter (FMC). Five kinds of large platelike particles of CaHPO4.2H2O (DCPD) after hydrolyzing at room temperature with different concentrations of NaOH aqueous solution ([NaOH]) for 1 h were used. DCPD converted completely to Hap after treatment at [NaOH]>or=2%, and the crystallinity of Hap was increased with an increase in [NaOH] up to 10%. The amounts of protein adsorbed (Deltanads) and desorbed (Deltandes) were measured simultaneously by monitoring the protein concentration downstream from the FMC with a UV detector. The Deltanads values were also measured statically by a batch method in each system. The Deltanads values measured by the FMC and static measurements fairly agreed with each other. Results revealed that DeltaHBSAads was decreased with an increase in [NaOH]; in other words, DeltaHBSAads was decreased with the improvement of Hap's crystallinity, suggesting that the BSA adsorption readily proceeded onto Hap. This fact indicated a high affinity of Hap to protein. This affinity was further recognized by DeltaHBSAdes because its positive value was increased by increasing [NaOH]. These opposite tendencies in DeltaHBSAads and DeltaHBSAdes revealed that Hap possessed a high adsorption affinity to BSA (i.e., enthalpy facilitated protein adsorption but hindered its desorption). The fraction of BSA desorption was also decreased with an increase in [NaOH], confirming the high affinity of Hap to protein. Similar results were observed on the LSZ system, though the enthalpy values were smaller than those of BSA. In the case of neutral MGB, DeltaHBSAads also exhibited results similar to those of the BSA and LSZ systems. However, due to its weak adsorption by the van der Waals force, DeltaHBSAdes was small and almost zero at [NaOH]>or=2%. Hence, the fraction of MGB desorption was less dependent on [NaOH].     

煤灰中矿物质组成对煤灰熔融温度的影响

选取九种不同灰熔融温度的煤样,利用X射线衍射分析方法,研究了煤灰的矿物质组成及含量对灰熔融温度的影响,以及弱还原性气氛下不同温度煤灰熔融过程中的矿物演变过程及其对灰熔融温度的影响。结果表明,815℃煤灰的主要晶体矿物质组成为石英、硬石膏、赤铁矿、氢氧钙石和石灰等。一般情况下,煤灰中氢氧钙石含量低,硬石膏和赤铁矿含量高的煤,灰熔融温度较低。在还原性气氛下,随着温度的升高,煤灰中的石英、硬石膏、氢氧钙石等结晶矿物含量逐渐减少,生成新的矿物质。莫来石的生成是导致煤灰熔融温度高的主要原因。低灰熔融温度煤灰在加热过程中,在1 100℃时,钙长石和铁钙辉石的生成起到了降低煤灰熔融温度的作用。     

Characterization of coal fly ash components by laser-induced breakdown spectroscopy

The high sensitivity of laser-induced breakdown spectroscopy (LIBS) for the detection of most of the fly ash components enables the analysis of these residues produced during the combustion of coal. Fly ash consists of oxides (SiO₂, Al₂O₃, Fe₂O₃, CaO…) and unburnt carbon which is the major determinant of combustion efficiency in coal fired boilers. For example, an excessive amount of residual carbon dispersed in the fly ash means a significant loss of energy (Styszko et al., 2004 [1]). Standard methods employed for the analysis of fly ash make not possible a control of boiler in real time. LIBS technique can significantly reduce the time of analysis, in some cases even an online detection can be performed. For this reason, some studies have been addressed in order to demonstrate the capability of the laser-induced breakdown spectroscopy technique for the detection of carbon content in high pressure conditions typical of thermal power plants (Noda et al., 2002 [2]) and for the monitoring of unburnt carbon for the boiler control in real time (Kurihara et al., 2003[3]).In particular, the content of unburnt carbon is a valuable indicator for the control of fly ash quality and for the boiler combustion. Depending on this unburnt carbon content, fly ash can be disposed as an industrial waste or as a raw material for the production of concrete in the construction sector. In this study, analyses were performed on specimens of various forms of preparation. Pressed pellets were prepared with two different binders. Presented results concern the nature and amount of the binder used to pelletize the powder, and the laser-induced breakdown spectroscopy parameters and procedure required to draw calibration curves of elements from the fly ash. Analysis “on tape” was performed in order to establish the experimental conditions for the future “online analysis”.     

Effect of sodium and calcium on the ash fusion temperatures of Zhundong coal

Journal of Thermal Analysis and Calorimetry - The effect of sodium and calcium on the ash fusion temperatures (AFTs) of Zhundong coal was investigated in this study using an ash fusibility tester...     

混煤燃烧过程中砷/硒与飞灰中矿物质之间的高温原位反应

为了研究混煤燃烧过程中痕量元素与飞灰中矿物质的原位反应，选取烟煤（HLH）、无烟煤（ZW）及其混煤在1150 ℃时的沉降炉中进行燃烧，并分别收集和分析了高温段灰分（HTA）和低温段灰分（LTA）中砷和硒残留率。结果表明，砷在高温段灰分中的残留率低于低温段灰，说明在烟气冷却过程中砷会被灰重新吸附。ZW、Z3H1、Z1H1、Z1H3、HLH的高温段灰中砷的残留率分别为60.31%、26.85%、13.29%、20.23%、36.11%，说明混煤的高温段灰比原煤更难捕获砷。同时，硒在五种煤样的高温段灰中的残留率分别为24.68%、23.60%、20.58%、15.19%和38.13%，其残留规律与砷相同。此外，X射线衍射（XRD）分析结果表明，混煤燃烧过程中矿物形态发生了明显变化。与原煤不同的是，混煤的HTA中出现了莫来石，且莫来石的峰值随着混煤中ZW比例的增加而增强。这与HTA中砷和硒的残留趋势一致。说明在混煤燃烧过程中，矿物质种类的变化以及矿物质与痕量元素的原位反应对砷和硒的排放有显著影响。     

Microstructure and phase characterizations of fly ash cements by alkali activation

Journal of Thermal Analysis and Calorimetry - Micro/mesoporous catalysts of ZSM-35/MCM-41 type were developed by mechanical synthesis method with the objective to use on the catalytic pyrolysis of...     

Instrumental neutron activation analysis of fly ash,aerosols and hair

Samples of coal, slag, emissions retained on the separating devices, fly ash, aerosols and hair taken in the area of coal-fired power plant were analyzed by means of instrumental neutron activation analysis. 13 to 23 elements were determined in the samples. The data obtained for emissions and aerosols were further evaluated by calculation of enrichment factors, correlation coefficients and by the ratio matching method. The concentrations of elements determined in the hair of exposed group were compared with the data of control and out control groups as well as with the recent data found for hair in other countries. It can be seen from the results that arsenic is the most serious pollutant in the area.