Stanislav S. Gornostayev

Behaviour of Coal associated Minerals during Coking and Blast Furnace Processes – a Review

Metallurgical coke is made from a mix of several types of coal that contain various minerals, including quartz, carbonates, feldspars, sulphides and a number of phyllosilicates, represented by clay minerals and micas. During coking and coke consumption processes the minerals undergo various physical and chemical changes, which in the case of coke oven batteries include desulphurization, decarbonation, dehydration, dehydroxylation, polymorph transformations, melting with the formation of an alkali and silica-rich liquid, and transformation to another crystalline phase. The typical modifications of mineral phases in a blast furnace (BF) coke are polymorph transformations, melting, and the formation of another crystalline phase. These events are also preceded by notable changes in the shape of crystalline aggregates. All these changes affect the coke properties and the processes occurring in a BF. Mineralogical data can help us to better understand the processes taking place in coke batteries and in a BF, and to improve the quality of a coke by more careful selection of coal blends and setting optimal temperatures for its pre-heating. The degradation of a BF coke by alkalis can be reduced by the addition of certain minerals to the feed coke before charging into the BF.

Sorosite, Cu(Sn,Sb), a new mineral from the Baimka placer deposit, western Chukotka, Russian Far East

Abstract Sorosite, ideally Cu(Sn5Sb), is a new mineral species from the Baimka gold-platinum- group mineral placer deposit, Chukotka, Russian Far East. It occurs as large subhedral to euhedral crystals (0.1-0.4 mm in length), hexagonal in cross section, minute crystals (≤ 15 μm, also hexagonal), and anhedral grains. Sorosite forms inclusions in Sb-bearing native tin, is often intergrown with stistaite (Sn1.12 - 1.13Sb0.87 - 0.88) and occurs with herzenbergite (SnS), native lead, and trace cassiterite. Sorosite is brittle with a microhardness VHN40;50 = 443.7 kg/mm2 (n = 3). No cleavage is observed. In reflected light, the large crystals are nearly white with a pinkish tint, whereas the microcrystals show a pronounced pinkish tint. Bireflectance is variable. The average of nine electron microprobe analyses gave Cu 35.33, Fe 1.18, Sn 58.18, and Sb 4.77, sum 99.46 wt%, corresponding to (Cu1.00Fe0.04)∑1.04 (Sn0.89Sb0.07)∑0.96. The powder pattern is close to those of natural Cu(Sn,Sb) and synthetic η-Cu6Sn5; it was indexed for a hexagonal cell, with a = 4.217(4) Å, c = 5.120(6) Å, and V = 78.85 Å3. For Z = 2, the calculated density is 7.6 g/cm3. The strongest lines in the pattern are at 2.970 (011), 2.112 (110), and 2.094 Å (012). The sorosite-bearing mineral assemblage apparently formed under low fO₂ and fS₂ conditions.

Fe-Si droplets associated with graphite on blast furnace coke

Fe-Si droplets on the surface of blast furnace (BF) coke from 25 to 50 cm at the tuyere level are mostly composed of Fe3Si, which has various shapes (round, elongated, and irregular) and penetration degrees into the BF coke matrix. The shapes and penetration degrees may depend on the saturation of molten iron by silicon during interaction with the coke matrix. The droplets are covered by a tiny shell of carbon. Graphite observed inside the droplets can be divided into two categories: well-formed tabular crystals with relatively large size and flakes with structures similar as those in cast iron. The textures of the droplets reflect composition, interaction with the coke matrix, and cooling conditions.

Textural changes in metallurgical coke prepared with polyethylene

The effect of high-density polyethylene (HDPE) on the textural features of experimental coke was investigated using polarized-light optical microscopy and wavelet-based image analysis. Metallurgical coke samples were prepared in a laboratory-scale furnace with 2.5%, 5.0%, 7.5%, 10.0%, and 12.5% HDPE by mass, and one sample was prepared by 100% coal. The amounts and distribution of textures (isotropic, mosaic and banded) and pores were obtained. The calculations reveal that the addition of HDPE results in a decrease of mosaic texture and an increase of isotropic texture. Ethylene formed from the decomposition of HDPE is considered as a probable reason for the texture modifications. The approach used in this study can be applied to indirect evaluation for the reactivity and strength of coke.

Fe−Si particles on the surface of blast furnace coke

This study investigates the surface of unpolished samples of blast furnace (BF) coke drilled from the tuyere zone, which hosts Fe-Si particles (mostly Fe3Si) that vary in size, shape, depth of submersion (penetration) into the coke matrix, and contact features with the surface. Based on the shape of the particles and the extent of their contact with the coke matrix, they have been grouped into three major types: (I) sphere-like droplets with limited contact area, (II) semi-spheres with a larger contact area, and (III) irregular segregations with a spherical surface, which exhibit the largest contact area among the three types of particles. Considering the ratio between the height (h) of the particles and half of their length at the surface level (l) along the cross-section, these three types can be characterized as follows: (I) h > l, (II) h ≈ l, and (III) h < l. All the three types of particles can be found near each other. The shape and the extent of the contact depend on the degree of penetration of the material into the matrix, which is a function of the composition of the particles. Type (I) particles were initially saturated with Si at an earlier stage and, for that reason, they can react less with carbon in the coke matrix than type (II) and (III), thereby moving faster through the coke cone. Thermodynamic calculations have shown that the temperature interval of 1250–1300°C can be considered the starting point for Si entering into molten iron under quartz-dominated coke ash. Accordingly, the initial pick-up of Si by molten iron can be assumed to be mineral-related. In terms of BF practice, better conditions for sliding Fe-Si droplets through the coke cone are available when they come into contact with free SiO2 concentrated into small grains, and when the SiO2/ΣMexOy mass ratio in the coke ash is high.

Carbon Tubular Morphologies in Blast Furnace Coke

The paper reports on the first occurrence of microscale carbon tubular morphologies (CMTs) in a blast furnace (BF) coke. The CMTs were probably formed as a result of the conversion of solid disordered carbon via liquid phase metal particles involving a gas phase containing a substantial amount of N2 and O2. The presence of CMTs may lie behind the generation of the smallest fraction of fines in BF exhaust dust. If the amount of CMTs present in the BF exhausts gases at any particular metallurgical site proves to be substantial, it could become a subject of environmental concern.

Effect of micro-pores on cracks formation in metallurgical coke

ABSTRACT The relationships of micro-pores and cracks in metallurgical coke have been investigated by optical microscope and field emission scanning electron microscope, using surface section samples. The pores have circular, elliptical and irregular shapes with smooth outlines, formed during the thermoplastic stage of the coking process. They often associate with connecting cracks between neighbouring pores. In case of elliptical pores, the connecting cracks are usually oriented along the longer axis of the pore. The connecting cracks can be developed between the pores, depending on their size and the distance between them. The coke with a large number of small pores rather than with a small number of larger pores will have lower strength due to the increased amount of connecting cracks. When compared with circular pores, elliptical and flattened pores have a lower ability to resist load pressure. Nano-sized pores have polygonal outlines, indicating an ‘explosion’-type formation in the solidified matrix. GRAPHICAL ABSTRACT