Influence of coal thermoplastic properties on coking pressure generation: Part 2 - A study of binary coal blends and specific additives

A number of coal blends and pitch/coal blends were evaluated using rheometry, thermogravimetric analysis and microscopy to confirm and further elucidate the coking pressure mechanism previously proposed by Duffy et al. (2007) [1]. We confirm that blending a low rank, high fluidity, low coking pressure coal, with a high rank, low fluidity, high coking pressure coal can significantly reduce the coking pressure associated with the latter. Interestingly, blending does not necessarily result in a fluidity that is midway between that of the two coals; sometimes the fluidity of the blend is less than that of the low fluidity coal, especially when the coals are significantly different in rank. This occurs because the increase in complex viscosity (η*) through resolidification of the low rank, high fluidity coal counteracts the reduction in η* resulting from softening of the high rank, low fluidity coal. It has also been confirmed that the η* of the resultant blend can be estimated from the η* of each component coal using a logarithmic additivity rule commonly employed for polymer blends.Polarised light microscopy has indicated that the degree of mixing between coals of different rank is minimal, with fusion restricted to the particle surface. It is therefore inappropriate to think of such a coal blend in the same way as a single coal, since each component coal behaves relatively independently. This limited fusion is important for understanding the coking pressure mechanism for blends. It is proposed here that the lower rank coal, which softens at lower temperature, is able to expand into the interparticle voids between the high rank coal that is yet to soften, and these voids can create channels for volatiles to traverse. Then, and importantly, when the high rank coal begins to expand, the pore structure developed in the resolidified structures of the low rank coal can facilitate removal of volatiles, while the resolidified material may also act as a suitable sorbent for volatile matter. This is considered to be the primary mechanism by which coal blending is able to alleviate coking pressure, and applies to addition of inert material also.Addition of a coal tar pitch was found to increase fluidity but also to extend the thermoplastic range to lower temperatures. This caused an increase in the swelling range, which was accompanied by a long plateau in η*, a feature which has previously been observed for certain high fluidity, high pressure coals. Elasticity and η* at the onset of expansion were also higher for both the pitch impregnated coals and the high pressure blends, which supports previous findings for singly charged high pressure coals, and confirms the potential use of such criteria for identifying potentially dangerous coals/blends.     

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.     

Influence of thermoplastic properties on coking pressure generation: Part 1 - A study of single coals of various rank

In this study a number of high coking pressure coals with different fluidities were evaluated alongside a number of low pressure coals also with differing fluidities. This was to confirm findings from an earlier study using a limited selection of coals, and to establish rheological parameters within which a coal may be considered potentially dangerous with regards to coking pressure. The results have confirmed and elaborated on previous findings which show that parallel plate displacement (ΔL) and axial force profiles can be used to distinguish between high and low pressure coals, with peak values indicating cell rupture and subsequent pore network formation. This is thought to correspond with plastic layer compaction in the coke oven.For low pressure coals pore coalescence occurs quite early in the softening process when viscosity/elasticity are decreasing and consequently a large degree of contraction/collapse is observed. For higher pressure coals the process is delayed since pore development and consequently wall thinning progress at a slower rate. If or when a pore network is established, a lower degree of contraction/collapse is observed because the event occurs closer to resolidification, where viscosity and elasticity are increasing. For the higher fluidity, high coking pressure coals, a greater degree of swelling is observed prior to cell rupture, and this is considered to be the primary reason for the high coking pressure observed with these coals. An additional consequence of these events is that high pressure coals are likely to contain a higher proportion of closed cells both at and during resolidification, reducing permeability in both the semi-coke and high temperature plastic layers, respectively.Using a rheological mapping approach to follow viscoelastic changes during carbonisation it has been possible to identify specific regions associated with dangerous coals. These tend to be fusible coals where at the onset of expansion, δ (elasticity) < 54° and η* (complex viscosity) > 5 × 10⁵ Pa s, and where in most cases δ_MAX does not exceed 65°.     

Interactions between coking coals and plastics during co-pyrolysis☆

Blends of three Australian coking coals and polypropylene, polystyrene, polyacrylonitrile and polyphenylene sulfide were prepared and the extent to which the blends fused on heating was monitored using proton magnetic resonance thermal analysis in order to identify interactions between them that could affect their fluidity. Different plastics had different effects. Polystyrene strongly reduced the fluidity of all of the coals, confirming previous findings. Polypropylene did not affect the fluidity of the two coking coals of lower rank. Polyphenylene sulfide reduced the fluidity of the coals at temperatures near the solidification temperature of the coals, and polyacrylonitrile appeared to increase the fluidity of the coals at temperatures near the softening temperature of the coals. The very different effects different plastics have on coal fluidity show that the interaction between plastics and coals must be carefully examined before plastics are added to coking coal blends.     

Influence of the permeability of the coal plastic layer on coking pressure

Ten coals of different rank and coking pressure characteristics were chosen in order to study the time of occurrence of the phenomena that take place during the coking of a coal and the way they affect the generation of dangerous coking pressures. Parameters derived from thermoplastic, thermogravimetric and permeability tests were studied together with semicoke contraction and the coking pressure generated by the coals in a movable wall oven. It was found that for safe coals, the maximum evolution of volatile matter occurs near the temperature of maximum fluidity. The position of the maximum rate of volatile matter evolution with respect to the zone of low permeability varies depending on the coking pressure characteristics of the coals. In addition, the relationship between the period of low permeability to the resolidification temperature may serve to indicate the degree of dangerousness of a coal. The fissure pattern of the semicoke was found to be related to the coking pressure and semicoke contraction.     

Understanding the mechanisms behind coking pressure: Relationship to pore structure

During carbonisation coal undergoes both physical and chemical changes that result in the generation of gas and tar and the formation of an intermediate plastic state. This transformation is known to generate high internal gas pressures for some coals during carbonisation that translate to high pressures at the oven wall. In this study, three low volatile coals A, B and C with oven wall pressures of 100 kPa, 60 kPa and 20 kPa respectively were investigated using high-temperature rheometry, ¹H NMR, thermogravimetric analysis and SEM, with the primary aim to better understand the mechanisms behind the coking pressure phenomenon. Rheometer plate displacement measurements (ΔL) have shown differences in the expansion and contraction behaviour of the three coals, which seem to correlate with changes in rheological properties; while SEM images have shown that the expansion process coincides with development of pore structure. It is considered that the point of maximum plate height (ΔL_max) prior to contraction may be indicative of a cell opening or pore network forming process, based on analogies with other foam systems. Such a process may be considered important for coking pressure since it provides a potential mechanism for volatile escape, relieving internal gas pressure and inducing charge contraction. For coal C, which has the highest fluidity ΔL_max occurs quite early in the softening process and consequently a large degree of contraction is observed; while for the lower fluidity coal B, the process is delayed since pore development and consequently wall thinning progress at a slower rate. When ΔL_max is attained, a lower degree of contraction is observed because the event occurs closer to resolidification where the increasing viscosity/elasticity can stabilise the expanded pore structure. For coal A which is relatively high fluidity, but also high coking pressure, a greater degree of swelling is observed prior to cell rupture, which may be due to greater fluid elasticity during the expansion process. This excessive expansion is considered to be a potential reason for its high coking pressure.     

Correlation of microstrength and industrial drum strength indices of metallurgical cokes

Correlations between microstrength and industrial drum strength indices of metallurgical cokes were obtained using a 230 kg coke oven. Twelve coking coals from different countries, and ranging in ASTM rank from hvA to Iv bituminous, were carbonized singly and in blends. Microstrength, JIS Drum and ASTM Drum tests were performed on the cokes produced. The results indicated that the relationship between the Dl¹⁵⁰₁₅ index and microstrength was non-linear. Correlation coefficients increased when highly fluid US hvA bituminous coals were excluded. The relationship between ASTM hardness and microstrength was less defined. Results of this study indicate that thermoplasticity is an important consideration when correlating microstrengths with industrial drum strengths.     

不同煤阶煤的CS2-NMP萃取率及与煤性质的关联

对6种不同变质程度煤(包括气煤、弱黏煤、肥煤、焦煤和瘦煤)常温常压下用CS2-NMP混合溶剂进行了萃取实验.结果表明,挥发分(Vdaf)为35%左右的煤具有最高的萃取率,达到43.05%,不同煤阶煤的萃取率与其奥压膨胀度及塑性温度区间近似呈线性关系.通过对原煤、萃取残渣和生成焦粒的红外对比分析表明,不同变质程度煤经过萃取后,残渣中脂肪烃和脂环烃含量有所减少,矿物质大都在残渣中,氢键缔合峰的强弱随不同煤种表现不同,肥煤和气煤氢键缔合的极性键都位于煤中的大分子上,而焦煤和弱黏煤中的极性键大都在小分子化合物上.     

Interactions between coking coals in blends

The thermoplastic behaviour of 78 binary blends of Australian coking coals was measured using proton magnetic resonance thermal analysis. Their measured extents of fusion were compared with the values calculated from measurements made on the component coals assuming additivity. Significant differences between calculated and measured results were found for most blends, though only at temperatures between 400 and 520 °C: the coals interacted at these temperatures in a way that affected their fluidity. Both positive and negative differences were observed. The magnitude of the differences increased both with increasing differences in rank between the coals and differences in fluidity between the coals. A statistical study of the differences showed that material that became fluid in coal at temperatures below about 360 °C did not appear to contribute to the interactions, which suggests that fluid material derived from liptinite plays a much smaller role in interactions than fluid material derived from vitrinite or inertinite. Additionally, the study indicated that the less fusible material in a blend slightly reduced the extent to which the associated more fusible material fused. It was not acting as an inert diluent.Fifteen blends of six Argonne premium coals were examined to see if the relationships found for Australian coals between the magnitude of the interaction and coal properties could be generalised. In most cases the agreement was good. However, at some temperatures, blends of Upper Freeport coal with lower rank coals were far less fluid than expected, suggesting that the fluidity of Upper Freeport coal is especially sensitive to these low rank coals.The general effect of interactions between coals of different ranks was to narrow the thermoplastic temperature range of the blend without reducing the maximum fluidity, in effect making the thermoplastic profile of the blend resemble the profile expected from an individual coal of the same average rank as the blend. The interactions are attributed to transfer of plasticising volatile material between the coals.     

Rheological properties of selected bituminous coals

The rheological behaviour of several bituminous coals has been evaluated by means of a constant torque Gieseler plastometer, utilizing both steadily increasing (3 °C min⁻¹) and isothermal (410 °C) temperature conditions. The results indicated that under either thermal treatment, the coals investigated showed predominantly pseudoplastic behaviour. The greatest degree of non-Newtonian behaviour occurred at or near the temperature of maximum fluidity for coals heated at 3 °C min⁻¹, or within the early stages of melting when isothermal heating was used. Empirical relationships relating the Gieseler fluidities to apparent viscosity were derived from the data.     

Plastic wastes, lube oils and carbochemical products as secondary feedstocks for blast-furnace coke production

Two plastic wastes (polyolefin-enriched and multicomponent), two lube oils (paraffinic and synthetic) and one coal-tar were assessed as individual and combined additives to coal blends for the production of blast furnace coke. The effects of adding 2 wt.% of these additives or their mixtures (50:50 w/w) on the coking capacity of coal, coking pressure and coke quality parameters were investigated. It was found that the two plastic wastes reduce fluidity, whereas the addition of oils and tar helps to partially restore the fluidity of the coal-plastic blend. From the co-carbonization of the coking blend with the different wastes in a movable wall oven of over 15 kg capacity, it was deduced that polyolefins have a detrimental effect on coking pressure. The addition of oils and tar to the coal-plastic blend has different modifying effects. Whereas paraffinic oil eliminated the high coking pressure caused by the polyolefins, polyol-ester oil had a weak reducing effect unlike coal-tar which had a strong enhancing effect. The compatibility of the oils/tar with plastics and coal and the beneficial influence of these combinations on coking pressure is discussed in relation to the miscibility of the plastic and the oily and bituminous additives, and the amount and composition of the volatile matter evolved from each additive during pyrolysis as evaluated by thermal analysis. Furthermore, it was found that coke reactivity towards CO₂ (CRI) and coke strength after reaction with CO₂ (CSR) are heavily dependent on the composition of the plastic waste, with polystyrene (PS) and polyethylene terephthalate (PET) having a clear negative effect. The porosity of the cokes obtained from blends containing plastic wastes is always higher, but the pores are smaller in size.     

Reactivity study of combustion for coals and their chars in relation to volatile content

To determine the effect of volatile matter on combustion reactivity, the pyrolysis and combustion behavior of a set of four (R, C, M and K coals) coals and their chars has been investigated in a TGA (SDT Q600). The maximum reaction temperatures and maximum reaction rates of the coals and their chars with different heating rates (5–20 °C/min) were analyzed and compared as well as their weight loss rates. The volatile matter had influence on decreasing the maximum reactivity temperature of low and medium rank coals (R, C and M coals), which have relatively high volatiles (9.5–43.0%), but for high rank coal (K coal) the maximum reactivity temperature was affected by reaction surface area rather than by its volatiles (3.9%). When the maximum reaction rates of a set of four coals were compared with those of their chars, the slopes of the maximum reaction rates for the medium rank coals (C and M coals) changed largely rather than those for the high and low rank coals (R and K coals) with increasing heating rates. This means that the fluidity of C and M coals was larger than that of their chars during combustion reaction. Consequently, for C and M coals, the activation energies are lower (24.5–28.1 kcal/mol) than their chars (29.3–35.9 kcal/mol), while the activation energies of R and K coals are higher (25.0-29.4 kcal/mol) than those of their chars (24.1–28.9 kcal/mol).     

Comparison of the associative structure of two different types of rich coals and their coking properties

Solvent extractions of two different types of Chinese rich coals i.e. Aiweiergou coal (AG) and Zaozhuang coal (ZZ) using the mixed solvent of carbon disulfide/N-methyl-2-pyrrolidinone (CS₂/NMP) with different mixing ratios were carried out and the caking indexes of the extracted residues were measured. It was found that the extracted residues from the two types of coals showed different changing tendencies of the caking indexes with the extraction yield. When the extraction yield attained about 50% for ZZ coal, the extracted residue had no caking property. However for AG coal, when the extraction yield reached the maximum of 63.5%, the corresponding extracted residue still had considerable caking property with the caking index of 25. This difference indicated the different associative structure of the two coals although they are of the same coalification. Hydro-thermal treatment of the two rich coals gave different extract fractionation distributions for the treated coals compared to those of raw coals respectively. The coking property evaluations of the two coals and their hydro-thermally treated ones were carried out in a crucible coking determination. The results showed that the hydro-thermal treatment could greatly improve the micro-strengths of the resulting coke from the two coals, and the improvement was more significant for the more aggregated AG coal. The reactivities of hydro-thermally treated AG coal blends were almost the same as those of raw coal blends. The higher coke reactivities of AG raw coal and its hydro-thermally treated ones than those of ZZ coal might be attributed to its special ash composition.     

基氏流动度指标特征分析

通过对炼焦煤基氏流动度指标、黏结性指标、镜质组反射率和挥发分等质量指标的研究,分析了不同煤种基氏流动度指标与其他黏结性指标和质量指标之间的关系,结果显示基氏流动度指标能够很好地反映炼焦煤的黏结特性,基氏流动度指标的最大流动度温度与炼焦煤变质程度呈现良好的相关性,可为炼焦煤质量的全面评价提供参考。     

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.     

The effects of impregnation of coal by alkali salts upon carbonization properties

The co-carbonization of coking and caking coals with potassium and sodium salts destroys the coking and caking capacities of the coals. Further, the resultant char is of high surface area and exhibits a high chemical reactivity to oxidizing gases because of the catalytic influence of potassium retained within the char.This article attempts to explain the above phenomena, i.e. the loss of coking mechanisms, the development of high surface areas and the retention of the potassium. Initially, current theories are outlined of coking mechanisms which establish the anisotropic, carbonaceous structural units within resultant cokes. These structural units are best observed as isochromatic areas in colours of blue, yellow or purple, using a polarized light microscope and a half-wave retarder plate in conjunction with polished surfaces of coke. When a coking coal is carbonized, it first softens and melts to form an isotropic, pitch-like fluid. On further heating, anisotropic units of irregular shape develop from within this fluid phase. In coal systems, these units grow to about 0.5–5.0 μm at which stage they join or fuse together but do not coalesce. Their identity is maintained, and they establish what are termed finemozaics. At the same time, the macro-properties of coke, e.g. porosity, are established.The formation of these anisotropic mozaics occurs via the growth of lamellar nematic liquid crystals containing stacked lamellar molecules. The liquid crystals possess the crystalline order which is transferred to the solid coke substance. It is the plasticity of the liquid crystals which allows the growing anisotropic units to fuse together, and the introduction of disclinations which impart desirable properties to the coke substance.The addition of potassium salts to coking coals is thought to reduce the fluidity of the coals primarily by increasing the number of cross-links which normally exists between the aromatic and hydroaromatic constituent molecules (building blocks) in the coal. Such an increase results, in turn, in an increase in molecular weight of the coal, decrease in its fluidity upon heat treatment, and the consequent decrease in mobility of planar regimes preventing their alignment to form the liquid crystals and then the anisotropic mozaics. It is suggested that the presence of potassium results in a higher oxygen content being present in the coal upon heating, either by reducing the rate of oxygen evolution from the coal as CO, CO₂ and/or water or by acting as an intermediate to extract additional oxygen from the steam added as a reactant to the system (that is, steam gasification). Thus, an increased oxygen content results in more cross-linking in the structure probably via ether linkages between aromatic and/or hydroaromatic regimes. This increase in cross-linkage creates the isotropic carbon of the char, the spaces between the cross-linked constituent molecules being microporosity responsible for the high surface area of the char. The potassium could be retained within the microporosity by being bonded to the oxygen attached to the carbon.     

Macerals in bituminous coals and the coking process: 2. Coal mass properties and coke mechanical properties

Bituminous coals produced in the Ostrava-Karviná coal basin show considerable variation in their maceral composition, vitrinite reflectance and fluidity. There is a close association of the latter with the $\text{H}\text{O}$ atomic ratio expressing the different chemico-structural properties of vitrinites of lower coalification. These properties of the coal mass all influence the coke mechanical properties; moreover the $\text{H}\text{O}{}_{\mathrm{at}}$ parameter is of principal importance to the course of the coking process. Laboratory, pilot-plant and full-scale experiments show that coals rich in inertinite may give cokes of suitable mechanical properties, providing the $\text{H}\text{O}{}_{\mathrm{at}}$, ratio and the bulk density are high enough. It should be noted, however, that these coals contain finely dispersed inertinite in the vitrinite mass and this may have a positive effect on the coke mechanical properties.     

基氏流动度在配煤炼焦中的应用

针对迁安中化炼焦煤采用常规煤质指标分析出现的单种煤常规指标较好,配煤炼焦后焦炭强度下降的问题,采用基氏流动度分析了常用两种中强黏结性炼焦煤A煤和B煤的煤质,探讨了其与常规煤质指标的关系,介绍了基氏流动度在配煤炼焦中的应用情况及存在问题。结果发现,A煤和B煤的常规煤质指标接近,最大基氏流动度分别为7209 ddpm和829 ddpm,可以较好区分两种煤;基氏流动度特征指标中的软化温度、塑性温度区间及最大流动度可反映炼焦煤的基本性质;炼焦煤的最大流动度的对数值在2.2~3.0、挥发分在23%~27%时,焦炭M40>87%、M10<7%。     

Influence of the size distribution of batch components on coke quality

Different degrees of crushing of coal in different technological groups, with constant rank and granulometric composition of the batch, significantly affect all the basic characteristics of coking: the packing density of the batch, the yield and strength (M ₂₅ and M ₁₀) of the coke, and its granulometric composition. That influence is practically always expressed through the products of factors (the contents of coals of different rank and different size class in the batch). This indicates systematic interaction of the components.