Structure in cokes from coals of different rank

A range of bituminous coals has been carbonized to 1273 K. Polished surfaces of the solid products, carbons or cokes, are examined for optical texture by optical microscopy. Fracture surfaces of the carbons are examined by scanning electron microscopy (SEM). The carbon from the lowest rank coal (NCB Code No. 702) is isotropic and fracture surfaces are featureless. Carbons from coals of ranks 602, 502 are optically isotropic but fracture surfaces are granular (size 0.1–0.2 μm), indicating small growth units of mesophase. In the carbon/coke from a 401 coal, the anisotropic optical texture and grain size are both ≈0.5–10 μm diameter. Coke from a coking coal (301a, 301b) has a layered structure extending in units of at least 20 μm diameter with sub-structures ~ 1.5 μm within the layers, indicating perhaps that the bedding anisotropy of these coals is not totally lost in the fluid phase of carbonization. The carbons from the higher rank coals have the bedding anisotropy of the parent coal. The combined techniques of optical microscopy and SEM (both before and after etching of the fracture surfaces of coke in chromic acid solution) reveal useful detail of structure in carbons/cokes and of the mechanism of carbonization of coking coals.     

The characterization of interfaces between textural components in metallurgical cokes

Six coals, representing the rank range normally encountered in commercial coking, were carbonized in a small oven to give dense cokes, of tensile strength comparable with that of good-quality blast-furnace coke. Interfaces between the different textural components in the cokes were studied by polarized-light microscopy. It proved possible to classify interfaces according to their perceived quality, to quantify their occurrence by point-counting and to calculate interface quality indices for the coke as a whole or for interfaces involving individual textural components. Interfaces between vitrinite-derived reactive coke components were superior to those involving inerts, but the inerts content of a coke did not have a marked influence on the coke interface quality index. The highest coke interface quality index was observed for the coke from the coal with the highest dilatation. No clear evidence of an influence of interface quality on coke tensile strength is apparent from the present data.     

Preliminary studies of the relation between the carbon texture and the strength of metallurgical coke

Preliminary attempts to relate the carbon texture to the tensile strength of metallurgical cokes are described. Two series of cokes made by carbonizing blended coal charges in pilot scale ovens were examined. The diametral compression test was used to determine the tensile strength of the cokes and the composition of the coke carbon was measured by applying a point-counting technique to the examination of atomic-oxygen etched surfaces. The strengths and textural compositions could be related by a single equation derived by multi-linear regression analysis.     

Bonding of solid additives in cokes from coals: a microscopy study

Cortonwood Silkstone (NCB class 401) and Betteshanger (NCB class 301 a/204) coals were co-carbonized with solid additives such as anthracite, coke breeze, green and calcined petroleum cokes. The resultant carbonization products (cokes) were examined by optical microscopy and SEM was used to investigate polished surfaces etched by chromic acid and fracture surfaces. For both coals only the anthracite and green petroleum coke become bonded to the coal cokes. This probably results from softening and interaction of interfaces of the anthracite and green coke with the fluid coal via a mechanism of hydrogenating solvolysis during the carbonization process. The coke breeze and calcined petroleum cokes were interlocked into the matrix of coal coke.     

Structure in metallurgical cokes and carbons as studied by etching with atomic oxygen and chromic acid

Anisotropie carbons and cokes exhibit an optical texture or micro-texture in the size range 0.5–300 μm in polished surfaces using optical microscopy. Structure within this optical texture can be studied as the topography created by etching surfaces with atomic oxygen and chromic acid. Atomic oxygen preferentially etches an isotropic carbon layer which exists between the grains of the fine-grained mozaics. Chromic acid oxidizes or etches selectively the surfaces of anisotropic carbon to create fissures parallel to basal plane orientation. Structural components within petroleum cokes, carbon fibres and carbon/carbon fibre composites are revealed. Chromic acid oxidizes isotropic components in metallurgi-cal cokes more slowly and so reveals the structure of cokes as prepared from co-carbonizations of coal with petroleum pitch. It is considered that these etching techniques augment our knowledge of internal structure within carbons and cokes and of considerations of strength and fracture in these materials.     

Effects of additions of petroleum coke in coals upon strengths of resultant cokes

Coals of NCB rank 301, 401 and 502 were co-carbonized with pitch-coke breeze pre-carbonized to temperatures between 900–1200 K, in the ratio 9:1. The objective was to provide fundamental information concerning the effect of inert components upon strength of metallurgical coke; these inert components occur naturally in coals and may also be added to coking blends as coke breeze. Polished surfaces of resultant cokes were examined by optical microscopy and fracture surfaces were examined by SEM to investigate the coal-coke/pitch-coke interface for bonding between components and fissure propagation across the interface. Strengths of cokes were measured using a micro-strength apparatus. For three coals, pitch-coke breeze (900 K and highest volatile content) bonded best to the surrounding coal-coke. The interface became increasingly fissured with increasing pre-carbonization temperature of pitch-coke.     

Binder—filler bonding in anode carbon Influence of filler coke surface

Bonding between binder and filler cokes in an experimental anode carbon, made using a coal-derived filler coke and a normal electrode-binder pitch, was investigated using scanning electron microscopy. The surface of each filler coke particle was found to contain rough and smooth areas formed respectively by breakage of the coke matrix during crushing and devolatilization pore formation during coal carbonization. Good bonding, indicated by continuity of structure, could be achieved between the fracture surfaces and granular or suitably aligned lamellar binder coke. Inadequate binder-filler bonding at smooth pore surfaces was evident by shrinkage fissures at the interface. The findings are explained in terms of the structures of the various types of carbon and the availability of edge carbon atoms for bond formation.     

Carbonization of coal blends: mesophase formation and coke properties

Laboratory investigations of strength of cokes from blends of coals incorporating pitch were supported by 7 kg trials. The stronger cokes showed a greater interaction between coal and pitch to produce an interface component of anisotropic mozaics which is relatively resistant to crack propagation. The process whereby coal is transformed into coke includes the formation of a fluid zone in which develop nematic liquid crystals and anisotropic carbon which is an essential component of metallurgical coke. Strength, thermal and oxidation resistance of coke can be discussed in terms of the size and shape of the anisotropic carbon which constitutes the optical texture of pore-wall material of coke. Coals of different rank form cokes with different optical textures. Blending procedures of non-caking, caking and coking coals involve the interactions of components of the blend to form mesophase and optical texture. Petroleum pitches used as additives are effective in modifying the carbonization process because of an ability to participate in hydrogen transfer reactions.     

Carbonization and liquid-crystal (mesophase) development. Part 4. Carbonization of coal-tar pitches and coals of increasing rank

Coal-tar pitches, from coals of different rank and with various quinoline-insoluble contents, were carbonized under pressure (67 to 200 MN m⁻²) to maximum temperatures of 923 K. The resultant cokes were examined by optical and scanning electron microscopy in terms of size and shape of anisotropic structures within the coke. Natural quinoline-insolubles and carbon blacks both destroyed growth of the mesophase and development of anisotropy. Graphite particles (<10 μm) promoted growth and coalescence of the mesophase. Fourteen coals, of carbon content 77 to 91 wt%, VM 41 to 26%, were similarly carbonized under pressure. In the lower-rank coals no microscopically resolvable anisotropic mesophase was produced, but at a carbon content of 85% anisotropic units 1–2 μm in diameter were detected, increasing in size at a carbon content of 90% to 5 μm diameter. Results are discussed in terms of the origins of anisotropic mosaics observed in cokes, their variation in size with coal rank, and their significance in the carbonization of coal.     

Carbonization and liquid-crystal (mesophase) development. 13. Kinetic considerations of the co-carbonizations of coals with organic additives

Five coals, of rank from an anthracite to a non-caking coal, have been carbonized singly and also cocarbonized with decacyclene, mixing ratio 7:3, in the temperature range 648 K to 823 K, heating at 10 K min^?1, with various soak times. The objective of the study is to derive the basic factors which influence the kinetics of formation of mesophase and anisotropic coke. Accordingly, resultant cokes were polished and surfaces examined by reflected polarized light in an optical microscope. The size, shape and extent of anisotropic development is discussed in terms of the conditions of carbonization and the rank of coal. In these systems a somewhat larger optical texture results in cokes produced at the higher carbonization temperatures. The temperature of onset of growth of anisotropic carbon in co-carbonizations was below that of either the coal or the decacyclene. Reactivities are evidently modified. The origins, growth and coalescence of growth units of anisotropic carbon in these cocarbonizations of coals with decacyclene are demonstrated.     

SEM characterization of cokes and carbons

Methods are described for the characterization of cokes and carbons in terms of their basic structural units — building blocks — as revealed by scanning electron microscopy of fractured and etched surfaces. Four basic forms of structural component are identified. These are termed flat, lamellar, intermediate and granular, according to their appearance in the fractured and etched surfaces. Fracture surfaces are considered to give the truer impression of the nature of these textural components but the proportion of the various components present is more readily determined from etched surfaces. The practical application of the technique in studies of the mechanical properties of metallurgical coke and anode carbon is described.     

A semi-industrial scale study of petroleum coke as an additive in cokemaking

The addition of petroleum coke to a typical industrial coal blend used in the production of metallurgical coke was studied. Cokes were produced at semi-industrial scale at the INCAR coking plant, using petroleum coke of different particle size distribution as an additive. Special attention was paid to changes caused in the textural properties (porosity, pore size distribution, fissures at the interface between metallurgical coke and petroleum coke) which have been found to be responsible for variations in the metallurgical coke quality parameters (e.g., mechanical strength and reactivity towards CO₂). Variation in porosity was found to depend on particle size and the proportion of the additive. The decrease in the microporosity (i.e., pore radius<3.7 nm) of the metallurgical cokes observed when petroleum coke is added to the coal blend, is postulated to be one of the main factors responsible for the decrease in the reactivity of these cokes. The variation of the mechanical strength indices can be explained by the changes in porosity and the quality of the interfaces between petroleum coke and metallurgical coke.     

Carbonization and liquid-crystal (mesophase) development. 21. Replacement of low-volatile caking coal by petroleum pitch in coal blends for metallurgical coke

Cokes were prepared in a 7 kg oven from blends of high-volatile and low-volatile caking coals, using ratios of 1:1 and 3:7. To the 1:1 blend was added 7.5% of either Ashland A240 or A170 petroleum pitch or SFBP petroleum pitch 1. Micum m₃₀ and m₁₀ indices were determined on cokes from the 7 kg oven, using the $\text{1}\text{5}$ Micum drum. Optical textures were assessed using polarized light microscopy of polished surfaces of cokes. The effect of additive is to increase the strength of cokes. The pitch can be an effective replacement of low-volatile caking coal. The analysis by optical microscopy shows that with the stronger cokes from the 7 kg oven there has occurred an interaction between the coal and pitch at the interface of coal particles to produce a solution or fluid phase which carbonizes to a coke with an optical texture of fine-grained mozaics. This material could be responsible for the enhancement of coke strength, being associated with pore wall material rather than with a change in porosity. The results agree with previous work using cokes prepared in the laboratory on a small scale.     

Study of the reaction of cokes with KOH under nitrogen

Five cokes of increasing content of anisotropic carbon were prepared. Polished surfaces of these cokes were characterized by optical microscopy in terms of components of optical texture. These surfaces were reacted with KOH at 873, 1073 and 1273 K in an inert atmosphere for 2 h and the resultant topography monitored by scanning electron microscopy (SEM). The extent of potassium take-up by coke particles was measured and the diffusion of potassium was detected by EDAX. Microstrength testing was made on the cokes before and after reaction with the alkali. Coke reactivity measurements were obtained for untreated and treated cokes. Results indicate that in an inert atmosphere the alkali reacts preferentially on the prismatic edges of anisotropic carbon and that the rates of reaction increase with increasing temperature. Potassium is able to diffuse into the interior of the more anisotropic coke particles and this casues weakening of the coke. The reactivity measurements indicate that for the more anisotropic cokes the effect of potassium as a catalyst in the solution-loss reaction is more pronounced than for the least anisotropic coke. These conclusions suggest that metallurgical coke in the blast furnace in the presence of alkali materials can lose strength by direct reaction over and above considerations of gasification processes.     

Influence of pitch additions on coal carbonization: Characterization of pitches

The technique of etching polished coke surfaces and examination by SEM was used to compare the abilities of a series of pitches to modify the carbon texture of cokes prepared from two low-rank coals. Cokes prepared from the pitches were similarly examined and a numerical texture index, the magnitude of which increased with increasing content of the larger textural components, was found to provide a useful measure of the ability of the pitches to modify the coke carbon texture.     

The influence of oxidation upon strength and structure of a needle-coke and a coal extract coke

Calcined commercial needle-cokes and coal extract coke are characterised by optical microscopy of polished surfaces. The needle-coke has an optical texture of coarse-grained mosaic, flow domain and a acicular flow domain; the coal extract coke has an optical texture of medium- and coarse-grained mosaics. The cokes are oxidised in air to 1–25% wt. loss. The microstrengths of original and oxidised cokes are measured. For the needle-cokes, a 1% wt. loss significantly reduces the microstrength values whereas for the coal extract coke the microstrength begins to decrease only after 15% wt. loss. SEM examination of original and oxidised surfaces indicates that oxidation of the needle-coke proceeds by the development of microfissures within the flow domain and by pitting of surfaces of the basal planes of the acicular flow domains. The surfaces of the coal extract coke were uniformly pitted. The decline of microstrength values of needle-cokes is associated with internal oxidation of the coke particles.     

Composition of pore-wall material in metal-lurgical coke: Considerations of strength,gasification and thermal stress

The optical texture of metallurgical cokes consists of anisotropic carbon made up of mozaics, 0.5–10 μm in size of flow-type anisotropy, 10–60 μm in size, as well as inert and isotropic material. Cokes from different coal sources possess optical textures which are different, being composed of different extents of the above components. The study examines the optical texture of polished surfaces of cokes and relates changes in surface topography caused by gasification by carbon dioxide at 1173 K, by heat treatment to 2073 k and by etching with atomic oxygen at 293 k to the optical texture. The results support a model to explain the strength of coke and its resistance to breakage caused by gasification, mechanical and thermal stresses, in terms of the size, orientation and bonding of the varied components which constitute the composite structure of coke material.     

Carbonization and liquid-crystal (mesophase) development. 10. The co-carbonization of coals with solvent-refined coals and coal extracts

Coals (NCB rank 102 to 902) were co-carbonized with solvent-refined coals and coal extracts, mixing ratio of 7:3, to 873 K, heating at 10 K min^?1 with a soak period of 1 h. Resultant cokes were examined in polished section using reflected polarized-light microscopy and optical textures were recorded photographically. These optical textures were compared to assess the ability of the additive pitch to modify both the size and extent of optical texture of resultant cokes. The objective of the study is to provide a fundamental understanding of the use of pitch materials in co-carbonizations of lower-rank coals to make metallurgical coke. A Gulf SRC was able to modify the optical texture of cokes from all coals except the anthracite. Soluble fractions of this Gulf SRC were less effective than the parent SRC. A coal extract (NCB D112) modified coke optical texture, the extent being enhanced as the rank of coal being extracted was increased. Hydrogenation of the coal extract increased the penetration of the pitch into the coal particles but simultaneously reduced the size of the optical texture relative to the non-hydrogenated pitch. This indicates a positive interaction of pitch with coal in the co-carbonization process. The optical texture of the cokes from the hydrogenated coal extract in single carbonizations was larger than that from the non-hydrogenated material. Mechanisms explaining these effects are briefly described.     

Impact of low-cost filler material on coke quality

An investigation was made to study the influence of low-cost filler material such as non-coking coals and refuse-derived fuel (RDF) on coke quality. Interfaces between textural components within the cokes were successfully characterised and the derived interface quality index showed some cokes contained more ‘good’ quality interfaces than others. The addition of filler coals and RDF to the coking coal increased the proportion of ‘poor’ interfaces’. A good correlation between coke strength, derived from a small drum test, and interface quality index was observed. During heat treatment of cokes at 1600 °C both metallic and non-metallic micro-constituents were found to undergo some transformation as revealed by the SEM surface morphology examination. Although heat treatment caused some fractures to enlarge and others to emerge, its effect on the quality of the coke was not significant. Based on the results from the samples studied, there were some indications of the potential use of RDF material in the production of coke as there were minimal adverse effects on the quality of coke produced.