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.     

A scanning electron microscope study of fractured and etched metallurgical coke surfaces

The object of this work was to attempt to link more closely coke strength and structure by establishing whether features visible on fracture surfaces could be identified with coke carbon textural constituents revealed either by polarized light microscopy of polished surfaces or by scanning electron microscopy of atomic oxygen-etched surfaces. The cokes used were produced in a laboratory furnace from coals covering the whole range or rank normally encountered in metallurgical coke production in the UK. Fracture surfaces were created by tensile fracture during diametral compression. In all three surfaces examined, the appearance of components derived from reactive coal constituents varied with the rank of the coal carbonized. A clear similarity was evident between features visible in the etched and fracture surfaces. The marked variation of fracture features imply that the textural composition of the coke carbon may make some contribution, as yet unquantified, to the variation in strength among cokes.     

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.     

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.     

Study of the relation between the phosphorus content of coal and coke

Established methods for the determination of phosphorus in coal and coke were compared and found to give results in satisfactory agreement. The method for the determination of phosphorus described in BS 1016, ‘Methods for the analysis and testing of coal and coke’, Part 9, 1977 was used to study the relation between the phosphorus content of coals and their corresponding cokes. The cokes were prepared on laboratory, test oven and industrial scales, by the carbonization of various bituminous coals within the range of volatile matter yield of 16–40 wt%. The determined values of the phosphorus contents of these cokes and their parent coals indicated that the phosphorus present in the coal is completely retained in cokes carbonized to temperatures between 900 and 1050 °C. On the basis of these experimental results it is suggested that the phosphorus content of coke can generally be calculated from a knowledge of the phosphorus content of the coal and the coke yield with an accuracy which is sufficient for normal requirements.     

The strength of industrial cokes. 6. Further studies of the influence of coke breeze in a coal charge on tensile strength of coke

The objective of this investigation was to ascertain if there was any pattern in the dependence of the tensile strength of coke on the proportion and particle size of coke-breeze in an oven charge and to establish if it was possible to interpret the changes in tensile strength in terms of coke structural features. Using a small-scale oven in order to obtain the optimum in close control of the charge preparation and carbonization conditions, cokes were prepared from each of two coking coals blended with coke breeze. The tensile strength of these cokes was determined by the diametrical-compression test and some details of their porous nature were determined from density measurements, mercury porosimetry and optical microscopy. The results clearly demonstrate that the tensile strength of coke is, in general, systematically reduced with increasing breeze content of the oven charge, the more coarsely ground breeze leading to a greater reduction of the tensile strength at any level of breeze addition. But very finely ground breeze at relatively low levels of addition can lead to an improvement in the tensile strength. These changes correlate with variations in the apparent density and the total porosity and possibly also with the average pore size.     

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.     

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 strength of industrial cokes. 7. Further studies of the influence of additives in a coke-oven charge on the tensile strength of coke

The objective of this investigation was to determine if the previously established dependence of the tensile strength of coke on the breeze content and particle size of coke breeze in the coke-oven charge was applicable to different types of breeze additives when used in a size range similar to that of commercial practice. Using a small-scale oven to obtain the desired close control of the charge preparation and carbonization conditions, cokes were prepared from a Yorkshire strongly-caking coal blended with either coke-oven breeze, petroleum-coke breeze, or silica sand. The tensile strength of the cokes was determined by the diametral-compression test and some details of their porous structure were obtained from density measurements and mercury pressure porosimetry. The results confirm that the tensile strength of coke varies systematically with the coke-oven breeze content of the oven charge, and in the present case, for a breeze of the particle size range used in commercial practice the tensile strength is increased at low additions and then progressively reduced at higher levels of addition. Different sources of coke-oven breeze behave in a similar manner and appear to act as an inert filler material. On the other hand petroleum-coke breeze additions progressively increase the coke tensile strength, the additive being bonded into the walls of the coke matrix. The changes in tensile strength are accompanied by systematic variations in apparent density and in porosity.     

The strength of industrial cokes. 5. Influence of coke breeze in a coal charge on tensile strength of coke

The purpose of this study was to determine the influence of different proportions and different particle sizes of coke breeze in a coke-oven charge on the tensile strength of the coke. The diametrical-compression test was used to determine the tensile strength of the coke produced in a 10-t test oven and the results obtained were considered in relation to the composition of the oven charge, the coke micum indices and to parameters describing the coke texture. It was established that breeze additions caused measurable but nonsystematic changes in the coke tensile strength and that decreasing the breeze particle size generally increased the coke tensile strength. These changes could not however be directly related to changes observed in the density, porosity, pore-wall thickness or mean pore size of the cokes. The previously established relations between micum indices and the tensile strength of foundry cokes were also found to be inapplicable. The conclusion was drawn that the behaviour described is associated with some, at present unestablished, factor of the blend composition, one possibility being the relative proportions and compatibility of the ‘binder’ and inert material acting through their influence on those aspects of the coke microstructure which control the coke breakage.     

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.     

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.     

Carbonization and liquid-crystal (mesophase) development. 20. Co-carbonization of a high-volatile caking coal with several petroleum pitches

A high-volatile caking coal and five petroleum pitches were carbonized singly and coal/pitch systems were co-carbonized to 1273 K in the ratio of 75 wt% coal and 25 wt% pitch. Optical textures of cokes from the single carbonizations and co-carbonizations are assessed in terms of modification to the coalcoke by the pitch and unmodified pitch-coke using a point-counting technique. The pitches differ considerably in their carbonization behaviour. Each pitch can be placed into one of three groups defined in terms of their interaction with the high-volatile caking coal. A passive pitch does not modify the coalcoke but apparently carbonizes independently of the coal. An active pitch modifies some of the coalcoke. No pitch-coke can be detected. A super-active pitch modifies the coal-coke extensively beyond the extent expected from a 25% addition. No pitch-coke can be detected. The effects are related to the ability of the pitch to cause depolymerization of the coal. Quinoline-insoluble material in pitch may inhibit modification.     

Co-carbonization of hard coals and coal extracts 2. The co-carbonization of medium- and high-rank coals with extracts

Studies on the influence of anthracene coal extracts on the carbonization process of medium- and high-rank coals were undertaken. Extracts from flame coal (Int. Class. 900) and gas-coking coal (Int. Class. 632) were used as additives. The blends prepared from the examined coals and the extracts exhibited better coking properties than the parent coals. The addition of extract to the coals gave an increase in the microstrength of the resultant cokes. The effects of co-carbonization of coking coals with extracts were increases in the size of the optical texture as well as in the degree of structural ordering of cokes. In the co-carbonization of semicoking coal with addition of coal extracts, a reduction in the size of the anisotropic units and a decrease in the crystallite height of cokes were observed. No modification of the basic anisotropy of coke from anthracite by coal extract was observed. With increasing extract content in anthracite/extract blends there was an increase in the degree of structural ordering of co-carbonization products. Extract addition was unable to modify the behaviour of fusinite. Based on the results of investigation of the influence of coal extracts on the carbonization of different-rank coals, a division of coals according to the modification of the optical texture of coke is given.     

Statistical analyses and prediction of coking properties of coal

Using regression analyses between the properties of coals and the strengths of their cokes several significant correlations are derived, which are useful to evaluate coals in the making of metallurgical coke. Slight but significant modification was necessary for their application to coal blends. For example, plasticities of the coal blends required a different equation from that derived for the single coals. The region of high coke-strength in the diagram of volatile matter vs. total dilatation was expanded considerably towards coals of lower caking properties by blending of coals, suggesting that the blending may serve to increase the coking properties of component coals. The coke strength, especially after the gasification was found to increase with the increasing inert maceral content in the parent coals up to 30 wt %. The high level of strength was maintained even above 35 wt % of inert content.     

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. 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.     

Carbonization and liquid-crystal (mesophase) development. 9. The co-carbonization of vitrains with Ashland A200 petroleum pitch

Vitrains from a wide range of ranks of coals were carbonized singly and also co-carbonized (HTT 1273 K) with 25% of Ashland A200 petroleum pitch. Polished surfaces of the resultant cokes were examined for optical texture in a polarizing-light optical microscope using a half-wave retarder plate to produce interference colours. For the anthracites, there is no modification of either component during co-carbonization. The growth of optical texture from the A200 pitch is not affected. For all caking vitrains the optical texture of coke from the blend system is extensively modified when compared to the optical texture of coke from the vitrain. For the low-rank non-caking vitrains the isotropic coke becomes totally or partially anisotropic in co-carbonization. The mechanism of modification of the optical texture of resultant cokes is related to the formation of nematic liquid crystals, mesophase and the semi-coke. It is not considered that the chemistry of pyrolysis is modified on cocarbonization of the vitrain and pitch.     

The co-carbonization of oxidized coals with pitches and decacyclene

Coals of rank (NCB) 701, 401 and 204 were oxidized in air at 371 K for up to 15 days. The changes in optical texture of cokes from these coals were monitored by optical microscopy and point counting. The oxidized coals were cocarbonized to 1273 K with up to 30% of A240 petroleum pitch, a hydrogenated coal extract and decacyclene, and the resultant cokes were reassessed. The increase in isotropy in cokes caused by the oxidation treatment was never completely removed by use of the additives, but significant improvements existed for the less extensively oxidized coals. The possibility exists of using co-carbonization of oxidized coals with additives in coke making. Additives with good hydrogen donor ability, as with the coal extract, appear to be the most suitable.     

Structure of cokes from coking coal vitrites

The coking process of vitrites and thermobitumens separated from vitrites was examined; structural X-ray and microscopic examinations of the cokes obtained were carried out. A correlation between reflectance distribution of vitrites and microscopic structure of their cokes was found.An increase in the structural ordering of the cokes from vitrites, passing from cokes of gas coal to cokes of orthocoking coals, is observed. It is accompanied by an increase of the optical anisotropy of the resultant cokes; this anisotropy first appears in coke from gas-coaking coal.The cokes from the thermobitumens are lower ordered than the cokes from parent vitrites but all these cokes are partially or entirely optically anisotropic.Total removal of the thermobitumens from coals deprives the cokes from the residues after the extraction of any optical anisotropy.