不同煤阶煤焦炭显微结构与热性质的研究

采用模拟焦炭反应性和反应后强度,研究了不同变质程度单种煤焦炭显微结构与热性质之间的关系。中等变质阶段的焦煤、肥煤和瘦煤所制焦炭有较高的各向异性,低变质程度的气煤、1/3焦煤以及高变质程度的贫煤所制焦炭各向异性程度较低。焦炭的热性质与焦炭的各向异性有很好的相关性,焦炭反应性随各向异性程度的增大而减小,反应后强度则随各向异性的增大而增大。     

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.     

Some aspects of changes in the macromolecular structure of coals in relation to thermoplastic properties

The development of coal thermoplasticity during the primary devolatilization region is critical in determining coke structures. The solvent swelling technique was used to study the changes in macromolecular structure of four coals of different rank (902 to 203 in the British Coal classification scheme) during carbonization to temperatures up to 600°C. The results were compared with the thermoplastic characteristics of the coals. The dilatometric and gas permeability properties are discussed in terms of changes in macromolecular structure. The study of the macromolecular structure provides new insight into the development of thermoplasticity and coke structure.     

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.     

Modification of sub-bituminous coal by steam treatment: Caking and coking properties

A Chinese sub-bituminous Shenfu (SF) coal was steam treated under atmospheric pressure and the caking and coking properties of the treated coals were evaluated by caking indexes (G_RI) and crucible coking characterizations. The results show that steam treatment can obviously increase the G_RI of SF coal. When the steam treated coals were used in the coal blends instead of SF raw coal, the micro-strength index (MSI) and particle coke strength after reaction (PSR) of the coke increased, and particle coke reactivity index (PRI) decreased, which are beneficial for metallurgical coke to increase the gas permeability in blast furnace. The quality of the coke obtained from 8% of 200 °C steam treated SF coal in coal blends gets to that of the coke obtained from the standard coal blends, in which there was no SF coal addition in the coal blends. The removal of oxygen groups, especially hydroxyl group thus favoring the breakage of the coal macromolecules and allowing the treated coal formation of much more amount of hydrocarbons, may be responsible for the modified results. The mechanism of the steam treatment was proposed based on the elemental analysis, thermo gravimetric (TG) and FTIR spectrometer characterizations of the steam treated coal.     

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.     

单种煤结焦性能评价与焦炭质量预测

根据11种单种煤的性质,在实验室20kg小焦炉上进行了11种单种煤和8种配煤方案的炼焦实验,并对焦炭进行了筛分组成、冷态强度、焦炭热性质等分析,初步建立了焦炭质量预测模型。实验结果表明:单一的煤质指标与焦炭强度的关系不是很明显,选用煤质多因素指标进行焦炭质量预测,其预测效果较好;单一的煤质指标(Vd、R0max、Ad)与焦炭反应性之间有较好的关系,且焦炭的反应性随反应温度的升高而增大。     

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.     

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.     

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.     

配合煤配比对焦炭综合热性质的影响

以企业生产实践为背景,研究在配合煤中增配肥煤和1/3焦煤对焦炭综合热性质的影响。对不同配比配合煤的性质指标进行检测,采用40 kg焦炉实施炼焦试验,并对炼制焦炭的传统国家标准热性质指标和利用自主研制装置测得的综合热性质指标进行测定。结果表明:增配肥煤和1/3焦煤,均会使配合煤的变质程度降低,挥发分含量升高,胶质体的黏结能力下降,但胶质体的量保持不变。配比变化引起的配合煤性质指标的变化没有显现在焦炭的传统国家标准热性质指标反应性CRI和反应后强度CSR上。以往的研究都是以CRI和CSR指标为目标量判断配合煤的配比是否合适,本研究除此之外还采用了自主提出的焦炭综合热性质指标。配合煤配比变化引起的焦炭的综合热性质指标变化比国家标准热性质CRI和CSR指标变化敏感,这可能与其反映了焦炭某些新的特征有关。基于焦炭综合热性质指标的变化规律,考虑到1/3焦煤具有经济性,生产上增配某些特定的1/3焦煤,可以同时达到提高焦炭质量和降低配煤成本的目的。     

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.     

Influence of coal forced oxidation on technological properties of cokes produced at laboratory scale

The effect of coal oxidation in air at 140 °C on the technological properties of cokes obtained at laboratory scale from two medium volatile bituminous coals has been studied. The proximate and ultimate analyses do not show important changes with coal oxidation time. However oxidation clearly has a strong effect on the plastic properties of the coals in view of the fact that the Gieseler fluidity eventually disappears. From this point variations in plastic properties can still be detected by FSI. Other changes, such as a shortening of the length of the saturated fragments of the aliphatic chains, a decrease in the aliphatic hydrogen content and an increase in the oxygen-containing groups are detected by PA-FTIR. It was also found that the main coke quality indices (mechanical strength and reactivity to CO₂) of both coke series are impaired with coal oxidation. A close relationship between reactivity to CO₂ and the micropore specific surface area of the cokes has been corroborated.     

Influence of coal forced oxidation on technological properties of cokes produced at laboratory scale

The effect of coal oxidation in air at 140 °C on the technological properties of cokes obtained at laboratory scale from two medium volatile bituminous coals has been studied. The proximate and ultimate analyses do not show important changes with coal oxidation time. However oxidation clearly has a strong effect on the plastic properties of the coals in view of the fact that the Gieseler fluidity eventually disappears. From this point variations in plastic properties can still be detected by FSI. Other changes, such as a shortening of the length of the saturated fragments of the aliphatic chains, a decrease in the aliphatic hydrogen content and an increase in the oxygen-containing groups are detected by PA-FTIR. It was also found that the main coke quality indices (mechanical strength and reactivity to CO₂) of both coke series are impaired with coal oxidation. A close relationship between reactivity to CO₂ and the micropore specific surface area of the cokes has been corroborated.     

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.     

Some physical properties of Canadian coals and their effects on coal reactivity

The pore volume, surface area and compressibility of eleven Canadian coals, varying in rank from lignite to semianthracite, have been determined by mercury porosimetry, gas adsorption method and relations derived from helium and mercury densities. The total pore volume was measured in the diameter range of 0.2 nm–2.98 μm, which was subdivided into two groups, namely the micropore region (< 0.0036 μm) and the combined meso- and macropore region (0.0036–2.98 μm). It has been determined that the porosity of the eleven coals studied varies from 2 to 39%. It has been found that the total pore volume, micropore volume, surface area and the apparent compressibility of these coals decrease with increase in the carbon content, or the rank of the coals. The effect of the total pore volume, micropore volume and surface area on chemical reactivity of the coal is discussed separately. A good correlation was obtained between the carbon content and helium density of the coal after correction is made for the mineral content.     

Influence of polyethylene terephthalate on the carbonisation of bituminous coals and on the modification of their electric and dielectric properties

The purpose of this research was to study the influence of 2 wt% of polyethylene terephthalate (PET) on carbonization of two bituminous medium-volatile coals being different in maximum fluidity (MF). During the research into consideration were taken the structure of the coal plastic layer, the value and the distribution of the intralayer pressure, the changes in volume of the heated coal charge and in the development of the porous structure of the coke, so the changes in electric and dielectric properties of the solid residues obtained from the co-carbonisation of the coals with PET and a coal-tar pitch.The investigations were carried out in a laboratory unit using X-raying and tracing the coal charge with markers of copper foil. Changes in the porous structure of the carbonized coals were estimated on the basis of micrographs taken with a scanning electronic microscope (SEM). It was established that under the influence of PET the thickness of the plastic layer of coals decreases; its zone structure modifies, value and the distribution of the intralayer pressure in the heated charge of bituminous coals changes. PET can change the mechanism of formation of coke obtained from coals with a lower MF index, which leads to appearance of a less dense coke. PET facilitates the formation of a denser coke when blended with a coal with higher MF.The change of electric and dielectric properties of co-carbonisation products of coals with PET and coal tar pitch is analysed. The analysis shows that PET reacts with coals with distinct MF indices in a different way and has an influence on them opposite to that of pitch. Namely: when blended with a coal of low MF, PET facilitates the formation of cross-links between the macromolecules, and with high MF—the processes of macromolecular chains' growth due to the increase in their length.     

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.     

Evaluating the mechanical properties of laboratory coke on the basis of the expansion-pressure dynamics of coal and coal mixtures

The production of coke with the specified mechanical properties mainly depends on the thermal destruction and clinkering of the coals in the plastic state. The properties of the plastic coal mass (viscosity, gas permeability, plastic-layer thickness, and temperature range of the plastic state) play a significant role in producing coke of specified quality [1–4]. This is because the porous structure of semicoke that will be converted to coke on subsequent heating is formed in the plastic state. Hence, other conditions being equal, the properties of coal in the plastic state may be used to evaluate coke quality (its mechanical strength).     

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.