Chemical transformation of iron compounds during the process of coal pyrolysis in steam

When the content of sulphur in hard coal is higher than 1.5% weight, such coal cannot be used as fuel in thermal-electric power stations due to environmental protection. Such coal can be used as a raw product in various chemical processes in which many valuable substances are obtained. This study is a small part of a major project looking for improved ways of utilizing sulphur-rich coals. Mössbauer measurements were carried out for semi-cokes obtained from sulphur-rich coal in the pyrolysis process in a steam atmosphere in the temperature range of 300–800 °C. Results of these measurements showed that during the pyrolysis process, pyrite transformed completely into iron oxides (magnetite and hematite), whereas illite transformed only partly even at the highest temperatures. Unfortunately, it was not possible to identify some products of the illite transformation.     

Chemical transformations of ferruginous minerals during the process of oxidation of hard coal

In this paper are given the results of Mössbauer measurements for three samples of coalWK22, MKL, WK16 in which respectively,pyrite, siderite andankerite were the predominant ferruginous minerals present. The results showed that these minerals are transformed tohematite during the oxidation process. A part of hematite appeared in the superparamagnetic phase when pyrite was present in the coal samples. The siderite was transformed to hematite but without the occurrence of its superparamagnetic phase.     

Kinetics of methane and tar evolution during coal pyrolysis

The first objective of this work was to compare the pyrolysis behavior of coals coming from different geographic locations (South Africa, South America, Europe, Australia, and North America). This preliminary study was limited to the kinetics of methane and tar evolution, with data on additional species to be reported in a separate publication. The second objective was to examine the possible relationship between tar and methane evolution during pyrolysis. This study was done by employing a thermogravimetric analyzer coupled with a Fourier-transform infrared spectrometer (TG-FTIR). The evolution curves for 35 coals of different elemental compositions were measured at three different heating rates (10, 30, and 100 K/min). Pyrolysis kinetics were described using a simple first-order reaction model. The technique, first proposed by Kissinger, is based on the variation of the temperature at which a volatile species evolution rate is a maximum (T_max) as a function of the heating rate. The TG-FTIR data for tar evolution reveal a generally consistent behavior for coals from different parts of the world, showing increasing activation energies with increasing coal rank. The same correlation is also true for methane, although the slope of the activation energy versus carbon content curve is rather flat, at least up to about 90% carbon content. The values of activation energies for methane evolution were found to be lower in the case of the Argonne coals, as compared with the non-US coals. A study of the temperatures at which the evolution of methane and tar begins (T_ini), and the temperatures at which the evolution rates reach a maximum (T_max), reveals a correlation between the T_ini for methane and T_max for tar. This may be due to the fact that both tar and methane evolve as a result of similar reactions involved in the breakup and recombination of the coal macromolecular network.     

Physics of coal methane: decisive role of iron compounds

The role of iron in formation of the coal methane is clarified based on the studies performed on the coal samples taken from different mines in Donetsk coal basin. Using Mössbauer spectroscopy, a correlation is found between the iron content and methane capacity of coal seams. By means of electron paramagnetic resonance, it is found that iron increases the concentration of non-compensated electron spins, i.e. dangled bonds at the carbon atoms. These bonds can be occupied by hydrogen atoms as a prerequisite of methane formation. The two-valence iron is shown to be the most effective in the increase of spin concentration. By using the ion mass spectrometry, the modelling of methane formation is carried out on the mechanical mixture of the iron-free reactor graphite, iron compounds and diluted sulphuric acid as a source of hydrogen atoms. The proposed mechanism is also confirmed by methane formation in the mixture of iron compounds and the coal from the mine where the iron and methane are practically absent.     

Laser pyrolysis of coal

A laser pyrolysis study was performed on No. 6 high volatile bituminous Illinois (USA) coal. Possible relationships between the elemental surface composition of solid samples and the variable output power and wavelength of the argon ion laser were observed. For wavelengths of 5017 Å and 5145 Å and incident powers of 0·24 and 0·54 watts, scanning electron microscopy coupled with X-ray energy spectral analysis indicated the highest content reduction in both organic and mineral sulfur.Mass spectroscopy was employed to analyze the composition of the evolved gases from laser pyrolysis of pulverized coal. Coal pyrolysis utilizing a 2·5 watt argon ion laser produced hydrogen sulfide through decomposition of pyritic sulfur FeS₂, or organic sulfur upon irradiation of the coal. Other gases such as methane and ethane were created with solid residues (tars and ash). Pulsed CO₂ laser irradiation of coal samples produced a solid residue having a different elemental composition than that of the original coal sample.     

Gamma-iron formation by reduction of iron compounds inherent in brown coal

The reduction of the iron compounds inherent in Victorian brown coal to form α-iron, γ-iron and cementite following heating to high temperatures under reducing conditions has been observed. It is probable that the γ-iron phase is responsible for the singlet reported in heat-treated coals.     

Insight into the calcium carboxylate release behavior during Zhundong coal pyrolysis and combustion

In this paper, the dynamic behavior of calcium carboxylate release during Zhundong coal pyrolysis and combustion is studied via reactive molecular dynamics (ReaxFF MD) simulation. The molecular structure model of Zhundong coal is constructed based on the combination of the classic Hatcher coal model and experimental characterizations. Pyrolysis simulations on the coal model are performed at different temperatures ranging from 2000 K to 2800 K. The pyrolysis experiments are also carried out to validate the ReaxFF simulation. The results show that most of the calcium are released into the volatiles by the thermal decomposition of CM-Ca (coal/char matrix with calcium bonded) after releasing CO₂. The distributions of the calcium bonded to gas, tar and inorganics as well as the atomic calcium in the volatiles are quantitatively classified. The thermal cracking of tar fragments are significant at high temperatures leading to the conversion of calcium from tar into the organic gas. Furthermore, the nascent char model is constructed to study the release behavior of calcium in char combustion stage. The calcium is initially released in the form of oxidized calcium and atomic calcium. With increasing temperature, the oxidized calcium trends to convert to the organically bonded calcium. By using the Arrhenius expression, the kinetic parameters for the release of calcium into various species during pyrolysis and char combustion stages are quantitatively determined.     

The iron mineral changes occurring in lignite coal during gasification

Representative lignite and gasified material samples were retrieved form a cooled down gasifier. The samples were taken at various heights in the gasifier that operated on lignite, under stable conditions. The proximate analyses, ash composition and temperature in the gasifier were determined according to standard procedures. The main minerals found in the present investigation were bassanite, illite, quartz, kaolinite, calcite and the only iron bearing mineral was found to be pyrite. The trend in the estimated particle surface temperature profile shows an increase in the drying, pyrolysis, gasification and combustion zones from about 300 °C to just over 900 °C. About 1/3 down the gasifier, an average particle temperature of about 400 °C and particle surface temperature of about 600 °C was measured where pyrite conversion started. About 2/3 down the gasifier, where an average temperature of about 700 °C and particle surface temperature of about 900 °C was measured, all the pyrite was converted and in the bottom part of the gasifier, oxidation of the iron started to play a role and hematite and an iron containing glass formed at an average temperature of > 800 °C and surface temperature of 900 °C.     

Chemical transformations in the zone of spall damageability

The results of experiments on studying the perlite–ferrite structure in steels under short-term negative pressures are described. It is shown that in the localized deformation bands formed in the zone of interference of unloading waves, where the tension stress is lower than the dynamic strength of the material, the cementite bands in perlite are crushed, their fragments are in part dissolved and enriched with carbon, and the cementite can pass into a steady spherical form on the boundary with ferrite. At relatively high shock-wave amplitudes, the perlite in its entirety acquires a spheroidal shape.     

Mechanism study of selenium retention by iron minerals during coal combustion

The interactions between selenium vapors and coal accessory Ca/Fe-minerals favor selenium emission control by transferring selenium into fly ash during coal combustion. Considering the complicated effects of iron transformation on selenium retention, iron species in fly ashes from seven coal-fired power plants were distinguished and the associations between selenium and iron minerals were assessed. Iron oxides (including Fe₃O₄, γ-Fe₂O₃ and ɑ-Fe₂O₃) were determined as the main form of iron minerals in fly ash. The adsorption of selenium vapors by different iron oxides was conducted at temperatures ranging from 300 to 900 °C and the species of captured selenium were identified. Furthermore, reaction sites on the surfaces of fresh and reacted iron oxides were compared to investigate the mechanism regarding selenium adsorption over these iron oxides, which were further clarified through density functional theory study. The results showed that iron oxides were surely to play a significant role in selenium retention mainly through chemisorption and the reactions probably occurred at temperatures below 900 °C. At 300 °C, ɑ-Fe₂O₃ had better selenium adsorption performance than Fe₃O₄/γ-Fe₂O₃. Regardless of iron species, Fe atoms on iron oxides participated in the selenium adsorption by forming a Se–O–Fe Structure. With temperature increasing, selenium adsorption by Fe atoms was suppressed, which caused a drop off in selenium capture capacity of Fe₃O₄ and ɑ-Fe₂O₃. Differently, increasing temperature promoted selenium adsorption over γ-Fe₂O₃, which owned a high selenium adsorption capacity even at 700 °C. Further analysis confirmed that the presence of O₂/H₂O(g) in the flue gas contributed to the formation of oxygen vacancies on the surface of γ-Fe₂O₃ at high temperatures and facilitated selenium vapors to react with Fe atoms.     

Structural transformations in single-crystal iron during shock-wave compression and tension: Molecular dynamics simulation

The molecular dynamics method is used to simulate shock-wave propagation in the [100] direction of a single-crystal bcc iron target in order to study structural transformations in compression and rarefaction waves and the mechanisms of spall fracture. The specific features of structural transformations near the lateral target surface have been analyzed.     

Filamentary iron nanostructures from laser-induced pyrolysis of iron pentacarbonyl and ethylene mixtures

In this work, we present results of the synthesis and characterization of iron and iron oxide nanoparticles aggregated in filamentary, spider-web-like structures. The particles were produced in a flow reactor by CO₂ laser pyrolysis of gaseous mixtures of iron pentacarbonyl and ethylene. Low- and high-resolution electron microscopy reveals chain-like structures of particles, most of them being composed of an α-iron core and an iron oxide shell, identified as magnetite and, to a lesser extent, hematite. These results are in good agreement with a M?ssbauer analysis carried out for the same samples. The role of the reaction temperature on the synthesis of filamentary iron nanostructures by infrared laser pyrolysis of Fe(CO)₅/C₂H₄ mixtures is discussed. Received: 31 May 2000 / Accepted: 6 June 2000 / Published online: 2 August 2000     

Sequence of transformations during ordering of nonstoichiometric compounds with the formation of M 3 X 2-type superstructures

A symmetry analysis of monoclinic, orthorhombic, and trigonal M ₃ X ₂-type superstructures, which can be formed in highly nonstoichiometric MX _y compounds with B1 structure, has been performed. Channels of disorder-order transitions MX _y → M ₃ X ₂ have been determined. It has been shown that two physically allowed sequences of transformations associated with the formation of M ₃ X ₂ superstructures are possible in nonstoichiometric MX _y compounds of Group IV transition metals with decreasing temperature, i.e., “cubic (space group \(Fm\bar 3m\) ) disordered MX _y phase → orthorhombic (space group Immm) ordered M ₃ X ₂ phase → orthorhombic (space group C222₁) ordered M ₃ X ₂ phase” and “cubic (space group \(Fm\bar 3m\) ) disordered MX _y phase → orthorhombic (space group Immm) ordered M ₃ X ₂ phase → monoclinic (space group C2) ordered M ₃ X ₂ phase.”     

A new insight into chemical reactions between biomass and alkaline additives during pyrolysis process

Understanding the chemical reactions during biomass and alkaline additives during pyrolysis process is critical to better utilization of biomass resource. In this study, the influence of seven alkaline additives (KOH, K₂CO₃, KHCO₃, CH₃COOK, NaOH, Ca(OH)₂, and Mg(OH)₂) on biomass pyrolysis was investigated in fixed-bed system, as well as the reaction mechanism through combining the evolution properties of biochar, bio-oil, gas products, and alkaline additives. Results showed that alkaline additives promoted the formation of biochar and gas products, while inhibited the generation of bio-oil. The content of phenols (reaching 80% for NaOH, mainly non?methoxy phenols) and hydrocarbons (reaching 38% for Ca(OH)₂, mainly aromatics) increased greatly at the cost of acetic acid and O-species. Carbon content of biochar decreased largely, while oxygen content increased greatly, and the main O-containing species were –OH, -O–CO and -COOH groups. The surface area of biochar also increased greatly (reaching 764 m²/g for KOH). During pyrolysis process, alkaline additives could react with high active O-containing species and carbon fragments to generate lots of vacancies, then some anions of alkaline additive quickly occupied these vacancies to form new O-containing groups in biochar. Alkaline additives also converted into more stable structure (K₂CO₃, Na₂CO₃, CaO, and MgO). The possible reaction pathway between biomass and alkaline additives was first proposed.     

铁冲击相变的分子动力学研究

用分子动力学方法模拟了单晶铁(Fe)在一定初始温度下冲击相变(α相→ε相)的微观过程，结果显示温度会导致冲击相变压力阈值降低.基于此微观过程，对加卸载波系的传播规律进行了相应计算和分析，结果表明在卸载过程中逆相变波(ε相→α相)相对于波前以当地纵波声速传播，而相对波后以亚声速传播，这可由卸载压力-密度曲线给出相应解释；计算了不同初态的卸载压力-密度状态曲线，并给出了逆相变带的分布，其分布规律显示了卸载过程逆相变的滞后现象. 关键词： 分子动力学 多体势 冲击波 相变     

Modeling char surface area evolution during coal pyrolysis: Effect of swelling and gasification at high pressures

In this paper, a previous model for char surface area change during atmospheric coal pyrolysis was modified to include the effect of particle swelling and gasification to predict the N₂ adsorption specific surface area of high-volatile bituminous char generated at high pressures with or without gasification. A correlation between the change of char surface area and P₀ΔV_P/m_cm (the ratio of the expansion work for particle swelling to the mass of metaplast cross-linked with coal matrix) was developed and analyzed. The number of the defect regions generated by gasification was considered in calculating adsorption sites quantitatively. Particle swelling opens (at P₀ΔV_P/m_cm<1350 J/kg) and then compresses (at 1350 J/kg <P₀ΔV_P/m_cm<10,000 J/kg) the space between metaplast clusters, making the N₂ adsorption specific surface area of char increase first and then decrease. After the gaps between metaplast clusters are filled, the specific surface area changes are minimal. Gasification generates new defect regions in clusters and reduces the clusters in char, making the specific surface area of char first increase and then decrease.     

Mössbauer studies of phase transformations in iron alloys

Procedures related to the preparation of samples for Mössbauer spectroscopy studies of phase transformations in metals research are discussed in examples of works undertaken by the authors; (i) determination of austempering kinetics of compacted graphite cast irons, (ii) CEMS studies aimed at finding suitable polishing treatments that reproduce the bulk phase proportions, (iii) CEMS investigations on samples polished by spark planing, and (iv) the research of surface processes produced by laser melting treatments.