Chemistry for Sustainable Development 16 (2008) 521-528 Content of Various Size and Density Particles in Cenosphere Concentrates of Volatile Coal Combustion Ashes from the Kuznetsk Coalfield

Abstract Using an aerodynamic method with the subsequent particle size analysis of the fractions obtained a separation process was carried out for cenosphere concentrates from volatile ashes of the Kuznetsk field coal combustion at the Moscow Thermal and Electric Plant TETs-22, the Belovo State Regional Power Station as well as for several cenosphere concentrate fractions obtained at the Novosibirsk Thermal and Electric Plant TETs-5. As much as 90 fractions with the various particle size (70-250 mm) and bulk density (0.16-0.52 g/cm 3 ) have been isolated from the concentrate of the Moscow TETs-22. Irrespective of particle size the bulk density of fractions with the maximal yield is equal to 0.33-0.35g/cm 3 , whereas the ratio of the apparent wall thickness to the particle diameter amounts to 0.042-0.043. The process of the aerodynamic separation of cenospheres from different concentrate sources can be satisfactorily described by theoretical dependences for the carryover of spherical particles; the deviations are caused, first of all, by a nonspherical shape of cenospheres

Influence of Temperature and Duration of α-Fe2O3 Calcination on Reactivity in Hydrogen Oxidation

Исследовано влияние температуры и продолжительности прокаливания однофазных образцов гематита со структурой α-Fe2O3 на окислительную способность в отношении водорода в режиме температурно-программируемой реакции в интервале 40–900 °C. Показано, что температура прокаливания является существенным фактором, влияющим на реакционную способность решеточного кислорода в окислении водорода. Образцы α-Fe2O3, прокаленные при 800–900 °C, проявляют наибольшую активность, процесс восстановления α-Fe2O3 в этих образцах протекает через стадию восстановления до магнетита, с последующим полным восстановлением до металла через совмещение стадий восстановления оксидов. Прокаливание образцов α-Fe2O3 при 1000–1100 °C приводит к существенному снижению окислительной способности, восстановление α-Fe2O3 начинается при температурах на 50–100 °C выше, идет без выделения отдельных стадий восстановления, полное восстановление α-Fe2O3 до металла в исследованных условиях не происходит. Установлено, что с увеличением температуры прокаливания образцов возрастает рентгенографическая плотность α-Fe2O3, что свидетельствует о снижении степени разупорядочения кристаллической решетки, которое приводит к росту энергии связи решеточного кислорода и существенному снижению реакционной способности α-Fe2O3 в окислении водородаThe effect of temperature and duration of calcination of single-phase samples of hematite with the α-Fe2O3 structure on the oxidizing ability with respect to hydrogen in the temperature-programmed reaction mode in the temperature range of 40–900 °C was studied. It is shown that the calcination temperature is a significant factor affecting the reactivity of lattice oxygen in the oxidation of hydrogen. Samples of α-Fe2O3, calcined at 800–900 °C, show the highest activity, the process of α-Fe2O3 reduction in these samples proceeds through the stage of reduction to magnetite, followed by complete reduction to metal through the combination of reduction stages of oxides. The calcination of α-Fe2O3 samples at 1000–1100 °C leads to a significant decrease in the oxidizing ability, the α-Fe2O3 reduction initiates at temperatures 50–100 °C higher, proceeds without separating individual reduction stages of oxide, there is no complete reduction of α-Fe2O3 under the studied conditions. It has been established that with an increase in the calcination temperature of the hematite samples, the X‑ray density of α-Fe2O3 increases, which indicates a decrease in the degree of crystal lattice disorder and an increase in the binding energy of lattice oxygen and manifests itself in a significant decrease in the reactivity of α-Fe2O3 in the oxidation of hydroge

The Composition, Structure, and Helium Permeability of Glass-Crystalline Shells of Cenospheres

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.The results of studying the relationship of the composition, structure, and the diffusive properties of glass-crystalline shells of cenospheres relative to helium are presented in a wide range of variations of macrocomponent and phase compositions, wt %: 58–68 of SiO2, 21–37 of Al2O3, 30–93 of glass phase, 1–50 of mullite, 0–15 of cristobalite, 1–7 of quartz, and 0–2 of anorthite. It is found that the helium permeability coefficients of the cenosphere glass phase exceed the similar values of silicate glass. The high level of permeability of cenosphere glass-crystalline shells ensures significant potential for their application as membrane elements of the diffusion–sorption technology of the selective recovery of helium from gas mixtures

Effect of HF Modification on the Catalytic Properties of Ferrospheres in the Oxidative Coupling of Methane

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.The effect of the HF modification of ferrospheres separated from fly ash after the combustion of brown coal on their chemical, phase compositions and catalytic properties in the oxidative coupling of methane was studied. The modification led to a change in the phase composition in comparison with that of the initial ferrospheres: a CaF2 phase appeared, the hematite phase content increased, and the ferrospinel content decreased. The yield of C2 hydrocarbons at 750°C increased by a factor of 1.5–2.0, and the fraction of ethylene in them increased to 30 or 65% at 750 or 850°C, respectively. It was assumed that an increase in the efficiency of HF-modified ferrospheres in the formation of ethane and its dehydrogenation into ethylene was due to the formation of oxyfluoride-type active sites. The pyrohydrolysis of fluorine-containing catalyst components at 850°C due to interaction with water vapor in a reaction atmosphere led to the formation of systems active in deep oxidation; this manifested itself in a sharp decrease in selectivity for the formation of C2 hydrocarbons and an increase in selectivity for CO2

Composition−Structure Relationship of Skeletal−Dendritic Ferrospheres Formed during Industrial Combustion of Lignite and Coal

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.The structure−composition relationship of skeletal−dendritic ferrospheres (FSs) isolated from fly ash from the coal and lignite combustion has been studied systematically by scanning electron microscopy (SEM) and energy-dispersive Xray spectroscopy. It is shown that illite is the aluminosilicate precursor determining the structure of globules in both cases. The formation of skeletal−dendritic globules occurs due to the “seed” of Al, Mg-ferrospinel that is formed in the thermochemical conversion of illite from initial coals. The dependence CaO = f(SiO2) that reflects the influence of glass-forming components reveals six groups of FSs, the composition of which is represented by linear regression equations. An analysis of SEM images of polished sections from six globule groups reveals that an increase in the concentration of glass-forming components in all groups is accompanied by gradual changes in the structure of globules, from the coarse-grained crystalline skeletal type to the finecrystalline dendritic type with a high content of the glass phase. The observed change in the structure is explained by expansion of the liquation region in the FeO−Fe2O3−SiO2 system, a rise in the oxidation potential, an increase in the proportion of ferrite complexes [Fe3+O2]− and [Fe23+O5]4− in high-calcium melts, and a decrease in the concentration of ferrospinel-forming Fe2+ and Fe3+ ions

Взаимосвязь состава и строения ферросфер скелетного и дендритного типов, выделенных из высококальциевых энергетических зол

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.This paper presents a systematic SEM–EDS study of polished sections of individual skeletal and dendritic ferrospheres in the –0.04 + 0.032 mm size fraction, isolated from fly ash from the combustion of brown coal from the Berezovskoe field. The ferrospheres are characterized by a wide range of variations in the macrocomponent composition of local areas. We have identified groups of globules whose overall composition as well as the composition of local areas on their polished sections can be represented by general equations for component concentrations: SiO2 = f(FeO), SiO2 = f(Al2O3), and CaO = f(SiO2). Such equations make it possible to identify the nature of the mineral precursors involved in the formation of the globules. FeO-rich skeletal ferrospheres with low CaO concentration originate from the thermochemical transformation of pyrite and illite associates. Skeletal and dendritic ferrospheres with monotonically increasing CaO and SiO2 concentrations are formed from pyrite and montmorillonite associates, with the participation of a melt containing quartz and decomposition products of Ca-humates of the initial coal. Skeletal and dendritic spinel ferrite crystallization is due to a magnesium aluminate spinel “seed,” resulting from the thermal transformation of illite and montmorillonite from the parent coal. The observed increase in glass phase concentration and the change from the skeletal type of crystallization to a dendritic in the ferrospheres containing ≤64 wt % FeO and ≥6.5 wt % CaO are due to the low concentration of the spinel-forming cations Fe2+ and Fe3+ in the melt and the increase in the percentage of [Fe3+O2]− and [Fe3+2O5]4− ferrite complexes with an increase in the degree of oxidation of the melt

Composition and Structure of the Shells of Aluminosilicate Microspheres in Fly Ash Formed on the Combustion of Ekibastuz Coal

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.A systematic study of the chemical and phase composition and structure of the shells of narrow fractions of nonmagnetic cenospheres separated from a concentrate of fly ash cenospheres from the combustion of pulverized SS (weakly caking coal) coal from the Ekibastuz Basin was carried out. It was found that the separated narrow fractions were characterized by a high Al2O3content of 33–38 wt %. The phase composition included 57–73 wt % vitreous phase, 25–40 wt % mullite, and 1.2–2.5 wt % quartz. An increase in the average diameter, thickness, and porosity of the glass-crystalline shell of globules with the concentration of aluminum was observed. Globules of the following two types were identified in the obtained fractions: spherical globules with an annular structure and foamy globules with a network structure formed from different illite and kaolinite mineral precursors, respectively

Composition–Structure Relationship of Skeletal–Dendritic Ferrospheres Formed during Industrial Combustion of Lignite and Coal

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.The structure−composition relationship of skeletal−dendritic ferrospheres (FSs) isolated from fly ash from the coal and lignite combustion has been studied systematically by scanning electron microscopy (SEM) and energy-dispersive Xray spectroscopy. It is shown that illite is the aluminosilicate precursor determining the structure of globules in both cases. The formation of skeletal−dendritic globules occurs due to the “seed” of Al, Mg-ferrospinel that is formed in the thermochemical conversion of illite from initial coals. The dependence CaO = f(SiO2) that reflects the influence of glass-forming components reveals six groups of FSs, the composition of which is represented by linear regression equations. An analysis of SEM images of polished sections from six globule groups reveals that an increase in the concentration of glass-forming components in all groups is accompanied by gradual changes in the structure of globules, from the coarse-grained crystalline skeletal type to the finecrystalline dendritic type with a high content of the glass phase. The observed change in the structure is explained by expansion of the liquation region in the FeO−Fe2O3−SiO2 system, a rise in the oxidation potential, an increase in the proportion of ferrite complexes [Fe3+O2]− and [Fe23+O5]4− in high-calcium melts, and a decrease in the concentration of ferrospinel-forming Fe2+ and Fe3+ ions

Composition, Structure, and Formation Routes of Blocklike Ferrospheres Separated from Coal and Lignite Fly Ashes

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.The structure−composition relationship of blocklike ferrospheres (FSs) isolated from fly ash from the coal and lignite combustion has been studied systematically by scanning electron microscopy and energy dispersive X-ray spectroscopy. Groups of globules for which the gross composition of polished sections corresponds to the general equations for the relationship of the concentrations SiO2 = f(Al2O3) and CaO = f(SiO2) are highlighted from FSs of two series. It is shown that blocklike FSs are formed during the sequential transformation of dispersed products of thermal conversion of mineral precursor associates: pyrite, quartz, and Ca, Al-humates in the case of brown coal; and pyrite, siderite, quartz, and calcite in the case of coal. Anorthite is the aluminosilicate precursor of blocklike FSs of both series. The dependence CaO = f(SiO2) that reflects the influence of glass-forming components reveals six groups of FSs. An analysis of SEM images of polished globule sections demonstrates that an increase in the concentration of glass-forming components in all groups is accompanied by gradual changes in the structure of globules, from a large blocklike type to a fine crystalline type with a high glass-phase content. The size and shape of crystallites are controlled by the size of a local melt area where the total concentration of spinel-forming oxides exceeds 85 wt %. An increase in the glass-phase concentration and a decrease in the crystallite size in globules with FeO ≤ 46−50 wt % are explained by expansion of the segregation region in the FeO−Fe2O3−SiO2 system as the oxidation potential rises