Carbonization of coals to produce anisotropic cokes. 2. Up-grading of modification activities of petroleum process residues and their correlation with structural parameters

Modifying activities of petroleum pitches and up-graded pitches in the co-carbonization with a range of coals have been examined with the object of proposing an effective co-carbonization process for blast-furnace coke production. Up-grading of additives was attempted using thermal, acidic and oxidative reactions. Acidic reactions with aluminium chloride were most effective with lighter petroleum residues of initially poor modifying activity, this being attributed to dealkylation, ring-closure and ring condensation reactions. The relation between modifying activity and structural indices is discussed. The aromaticity (f_a) and the naphthenic ring number in the unit structure T_n,us can be used as appropriate parameters for the activity when the coking yield is taken into account.     

Carbonization of coals to produce anisotropic cokes.: 4. Improving co-carbonization behaviour of bituminous and subbituminous coals with pitch by pretreatment coals to remove cations

Several de-ashing pretreatments of selected coals have been examined to establish simple and effective procedures to improve, in terms of anisotropic development, the co-carbonization behaviour of the coals with pitches. Refluxing pretreatments of the coals in 1N HCI containing methanol and in boiling water containing EDTA-2Na (EDTA-2Na/coal = 7/100 byweight) improve the co-carbonization behaviour of Witbank, Miller, Taiheiyo and Wandoan coals, all of which, in their original, untreated form, are modified in terms of anisotropic development only very slightly in co-carbonizations with A240 petroleum pitch. Pretreatment of coals of very low rank appears to be ineffective in co-carbonizations with A240; however, co-carbonization with hydrogenated A240 shows that the pretreatments are effective. Analyses and FT-i.r. spectroscopy of mineral matter suggest that improved behaviour due to the pretreatment is related to the removal of divalent cations and to the modification of the oxygen functionality of the coals.     

Carbonization of coals to produce anisotropic cokes: 3. Evaluation of low-rank bituminous and subbituminous coals by single and co-carbonizations with pitch

Single carbonizations and co-carbonizations of 17 low-rank bituminous and subbituminous coals have been studied to evaluate their suitability as sources of blast furnace coke in terms of pore-wall profile and anisotropic development within the cokes. Co-carbonizations suggest the possible use of low-rank coals which from single carbonizations would not have been considered suitable. To evaluate semi-quantitatively the coke quality, two structural characteristics of the cokes produced by single and co-carbonizations are graded on a scale of 1 to 5. Overall assessments for each coal are plotted against the atomic H/C and 0/C ratios of the original coals. Although there are a few exceptions, coals with similar assessments are located in the same region of the plot, indicating that, to a first approximation, the H/C and 0/C ratios are suitable indicators of the single and co-carbonization properties of a coal. The presence of cations in the coal appears to be an additional factor influencing the carbonization properties and may explain the exceptional behaviour of some coals. Removal of these cations by pretreatment of the coals improves the carbonization properties.     

Carbonization of coals to produce anisotropic cokes: 5. Structural factors of coals influencing carbonization properties

The carbonization properties are studied of two particular coals (Zontag Vlei and Metla coals) which are markedly different despite their similar coalification rank, maceral composition, and oxygen and exinite contents. These coals possess different structural features which influence their carbonization. A demineralizing pretreatment improves the properties of Metla coal. However, this is still inferior to the Zontag Vlei coal. O-alkylation of the Metla coal improves fusibility in single carbonizations and susceptibilities, equalling those of the Zontag Vlei coal. Preheat-treatment differentiates between the coals: Metla coal loses its susceptibility at lower temperatures. The chemical analyses of oxygen functionalities of both the original and preheated coals show that their hydroxyl groups behave differently in carbonizations at lower temperatures, indicating that oxygen functionality may be another influential factor. Hydrogen shuttling within the coal may be a third factor as it may remove the oxygen functionality.     

Carbonization of coals into anisotropic cokes: 6. Formed cokes of high density and optical anisotropy from non-fusible and slightly fusible coals

A procedure for the preparation of solid formed coke of enough adhesion and anisotropic development for use in the blast furnace has been studied, using non-fusible and slightly fusible coals with petroleum cocarbonizing additives. The coke precursor was prepared through the copreheat-treatment of coal and a suitable additive in adequate quantity under stipulated conditions. The desired coke was produced by carbonization after forming with a press. The conditions for the copreheat-treatment have been carefully examined in terms of the temperature, time and heating devices. The behaviour of coals during copreheat-treatment and carbonization were discussed in terms of coal ranks, comparing this behaviour to the liquefaction reactivity and thermal stability of their liquefied product.     

Carbonization of coals into anisotropic cokes: 7. Copreheat-treatment under short contact-time conditions at high temperature

The copreheat-treatment of non-fusible and slightly fusible coals with A240 and hydrogenated A240 under high temperature-short contact-time conditions around 500 °C has been examined in an attempt to produce a formed coke with better anisotropic development. These conditions shortened the copreheat-treatment time and provided better anisotropic development in the resultant coke after carbonization. Effectiveness of short contact-time has been discussed in terms of the extent of depolymerization of coal molecules suitable for anisotropic development, this being related to coal liquefaction under similar conditions.     

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.     

Carbonization reactions of inertinite macerals in Australian coals

Widespread disagreement about the degree of reactivity of the inertinite group of macerais is related to variations in experimental conditions of assessment and failure to appreciate technological modifications imposed on similar macerals by dissimilar source materials and depositional conditions. This has resulted in the constant under-estimation of the coking potential of post-Carboniferous inertinite-rich coals by predictive methods developed for vitrinite-rich Carboniferous coals. Coking tests up to 1000 °C have been carried out on 20 coals of different rank in such a manner that coked portions of the samples could be correlated with their uncoked equivalents. It has been found that an inverse relationship exists between the level of precarbonization reflectance (PCR) of inertinite and the reflectance and bireflectance of its coke. The increase in the latter parameter is non-linear and involves a sudden jump which is taken as the boundary between reactive (high bireflectance) and non-reactive (low bireflectance) inertinite. In relation to coal rank a reactivity field for inertinite has been delineated which can be subdivided into two areas of high and moderate reactivity, respectively. On the whole, the proportion of reactive inertinite is larger than allowed for in most petrography-based coke stability calculations.     

Carbonization of coals into anisotropic cokes: 8. Carbonization of a canadian weathered coal into anisotropic coke

The carbonization properties of a weathered high rank bituminous coal were compared with those of the non-weathered coal. The weathering decreased the fusibility of the coal to leave more basic anisotropy and to diminish the size of the majority of the anisotropy in the resulting coke. On the other hand, more domain and flow domain textures developed. Co-carbonization with a petroleum pitch additive (Ashland A240) was found effective in enhancing the fusibility of the coal and anisotropic development in the coke. Formed coking of the weathered coal by means of copreheat-treatment with the additive, provided an anisotropic, dense and strong coke of uniform size. For the weathered coal, the optimum copreheat-treatment was shorter than that using the non-weathered coal indicating high coking reactivity of the weathered coal. The transferable hydrogens from the additive are rapidly consumed by the oxygen containing groups of the weathered coal.     

Applications of laser Raman microprobe spectroscopy to the characterization of coals and cokes

Optical microscopy is widely used in the characterization of coals and cokes. This Paper shows that the laser Raman microprobe (MOLE) which combines an optical microscope and a Raman spectrometer can provide useful additional information. Three main areas were investigated: identification of minerals in coal and coke; structural characterization of coals and cokes; and the interaction of inorganic additives and coal. Where possible, the results were compared with conventional optical microscopy measurements whereby it was shown that the optical texture and Raman spectra of cokes are not closely related. The Raman spectra of high temperature cokes were used to estimate the size of microcrystalline regions.     

Ultimate analysis of coals and cokes using instrumental techniques

This Paper describes instrumental techniques for the rapid determination of carbon, hydrogen, nitrogen, oxygen and sulphur. Two Perkin-Elmer Model 240 elemental micro-analysers were used, one for the direct determination of oxygen and the other for the simultaneous analysis for carbon, hydrogen and nitrogen. The Leco Automatic Sulphur Titrator was used for the sulphur assay. Accuracy and repeatability similar to that obtained by the classical methods described in the relevant British Standards were found, and data are presented to illustrate the comparison. Special aspects of developed procedures are emphasized which are essential for the attainment of good precision and accuracy.     

单种煤性质对其焦炭性质的影响

通过测定11种单种煤和所炼坩埚焦的性质，得出单种煤挥发分与平均最大反射率在合适的范围内，所炼坩埚焦的反应性最小，结构强度最大。     

Properties and potential of formed cokes derived from two Turkish lignites by carbonization of binderless briquettes

Two high-sulphur Turkish lignites were briquetted at room temperature under pressures of 113 or 212 MPa and the briquettes were carbonized to 1158–1173 K over special heating cycles. The lower-rank lignite gave a formed coke of superior mechanical strength, lower porosity and higher sulphur content than typical blast furnace cokes. The formed coke produced from the higher-rank lignite briquettes had slightly poorer mechanical strength, lower porosity and much higher ash yield and sulphur content than conventional cokes. The products were considered attractive for use in non-ferrous metallurgy.     

Carbonization and liquid-crystal (mesophase) development. 11. The co-carbonization of low-rank coals with modified petroleum pitches

Coals of rank ranging from medium quality coking to non-caking, non-fusible, have been co-carbonized with Ashland petroleum pitches A170, A240 and A200 as well as pitches modified by heat-treatment with aluminium chloride using A170, and by reductive hydrogenation of the A200. The mixing ratio was 7:3, the final HTT was 873 K, heating at 10 K min^?1 with a soak time of 1 h. The optical texture of the resultant cokes is assessed using polished surfaces and a polarized-light microscope using reflected light and a half-wave plate. The changes in optical texture are studied from the point of view of using coals of low rank in the making of metallurgical coke. The optical texture of resultant cokes is modified by co-carbonization and the mechanism involves a solution or solvolysis of the non-fusible coals followed by the formation of nematic liquid crystals and mesophase in the resultant plastic phase. The modified A170 pitch is more effective in modifying optical texture than the A170 because of an increase in molecular weight. The hydrogenated A200 is a very reactive additive probably because of an increased concentration of naphthenic hydrogen. The hydrogenated A200 can modify the optical texture of cokes from the organic inerts of coals and from oxidized, non-fusible coals.     

Influence of the oxygen content of low-rank coals on the development of porosity during carbonization

The development of porosity in the course of carbonization of a flame coal, original and pre-oxidized, was studied by means of the adsorption of benzene and carbon dioxide. The results were compared with corresponding data for cokes from a xylitic brown coal. The influence of coal oxygen content on the formation of coke porosity and its thermal dependence is discussed.     

Carbonization and liquid-crystal (mesophase) development. 12. Mechanisms of the co-carbonization of coals with organic additives

In industrial situations, coals interact with solvents or additives to produce liquid fuels, solvent-refined coal, coal extract and metallurgical coke. In these processes there occurs a wide variation in effects or modifications of the coal by these additives. This paper describes the modifications which can occur, using a wide range of rank of coal, when these coals interact and are co-carbonized with a wide range of additives of different chemical properties. The optical texture of the resultant cokes is given special attention. The objective of the paper is to summarize the current state of knowledge of the mechanisms of these interactions. Possible mechanisms of interactions are summarized, kinetic and chemical structural aspects of reactions are outlined, the importance is mentioned of the formation of liquid phases enabling anisotropic optical textures in modified cokes to be created, and the industrial relevance of its possible development is discussed.     

Effect of low-volatile additives on the structure and strength of cokes

Blends of medium-volatile or high-volatile coals have been carbonized in a 7 kg oven with low-volatile coals (6–16% VM, dmmf). A comparison is made of the strength and structural properties of these cokes with those of the cokes made under corresponding conditions from the medium or high-volatile coals alone. With increasing levels of addition of the low-volatile coals the tensile strength of the blend cokes generally attains a maximum and then decreases. These strength changes are related to changes in porosity, pore-wall thickness and pore dimensions. Coals which display some degree of plasticity and which are weakly caking improve coke quality by altering the pore-structure due to the combined effects of decreasing the pore diameter and slightly increasing the wall thickness. Those additives which are non-caking act primarily as wall thickeners.     

Aspects of gasification and structure in cokes from coals

Cokes were prepared from nine coals of different rank and characterized by surface area measurement, reactivity to carbon dioxide at 1473K and Raman-laser spectroscopy. Rates of gasification of cokes on a unit surlface area basis (K¹ = g m^?2 min^?1) decreased with increasing rank of parent coal based on maximum oil reflectances. However rates of gasification could not be related to coke structure as measured by Raman-laser spectroscopy.     

Carbonization properties of hydrogenated aromatic hydrocarbons—III: Modifying activities of hydrogenated pryene and its oxidized derivatives in the co-carbonization of coals and coal liquids

The modifying activities of hydrogenated pyrene (HP) and its oxidized derivatives were examined in co-carbonization with solvent refined coal, solvent treated coal, a fusible and a non-fusible coal. The present additives all showed a significant activity, with HP oxidized at 150°C exhibiting the highest activity. The activity of the additive is discussed from its structural indices and coke yield in relation to its dissolving and hydrogen donating abilities. The modifying susceptivility of the carbonizing substance is rated in the order described above, being correlated with its single carbonization properties, such as fusibility and potential for anisotropic development. A consecutive treatment of partial hydrogenation and oxidation is emphasized as a useful technique for producing active additive and an excellent coking substance from the pitch material.     

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.