煤的变质程度对焦炭性质影响的研究

对不同变质程度的5种烟煤进行了5 kg实验焦炉炭化实验.并就单种煤的结焦性与对应焦炭的微晶结构间的关系进行了探讨.结果表明,1/3焦煤焦炭、焦煤焦炭的冷态强度和热态强度较好;X射线衍射(XRD)分析结果表明,肥煤焦炭的炭结构因子(La/Lc)最小,石墨化程度最高.焦炭的真相对密度(TRD)随着La/Lc的增大而减小.     

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。     

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.     

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.     

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.     

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.     

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.     

Mild coal extraction for the production of anode coke from Blue Gem coal

The quality and availability of petroleum coke used in the manufacture of carbon anodes for aluminum production is a growing concern to the industry. Coke quality and yields have progressively declined as changes in refinery practice and the move towards processing an increasing proportion of heavier sour crudes have affected coke properties, resulting in an increase in the metal impurities and sulfur content of the coke. An alternative supply of anode coke is required to supplement or eventually replace calcined petroleum coke. The significant domestic reserves of coal could represent a viable carbon resource for anode production, provided defined coke specifications can be met and at a cost that is economically viable.The principal objective of this study was to examine the feasibility of producing anode grade coke by the UKCAER process for the mild solvent extraction of coal. Blue Gem coal from Eastern Kentucky was dissolved in a high boiling point solvent, the mineral matter and unreacted products removed by filtration, and the clean coal liquid converted to coke. The performance of the coal in solvent extraction was compared to a very reactive coal from Western Kentucky. A simple solvent-extraction screening test was established to assess potential candidate materials and process variables without the need for prolonged and complex routines. The coals were assessed in more detail to determine the optimum process conditions by conducting larger scale extraction tests to yield sufficient material for conversion to coke. The green cokes were calcined and the products characterized. The composition and structure of the calcined cokes were compared to typical petroleum coke and assessed for their use in the fabrication of carbon anodes.     

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.     

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 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.     

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.     

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.     

Coal rank and coke reactivity

For a series of cokes prepared under identical carbonizing conditions it was shown that rates of reaction with carbon dioxide/nitrogen mixtures at about 1000°C were generally higher for the cokes prepared from coals of above 30% volatile matter. The reaction rates of cokes prepared from certain Durham coals were generally higher than anticipated. Gasification of cokes prepared from certain Durham coals were generally higher than anticipated. Gasification of the cokes resulted in loss of strength, decrease in apparent density, enlargement of pores and reduction of pore-wall thickness. It appeared that burn-off was primarily associated mineral constituents of the coke ash upon gasification rates was detected. A tentative relation was derived between gasification rates and the ratio of pore-wall thickness to pore diameter of the cokes. In turn, this latter ratio appeared to bear some relation to the oxygen content of the coal. The majority of the parameters studied were measured by established techniques. Porosity was determined by mercury pressure porosimetry and the Quantimet 720 automatic image analysis microscope was employed for structural studies. The accuracy of the measurement of pore and pore-wall dimensions was approximately ± 2%.     

煤种及炭化条件对活性焦表面化学性质的影响

在不同煤种及炭化条件下,于一间歇流化床上制备活性焦(AC)。使用XPS等分析手段考察不同制备条件下制得的活性焦表面化学性质的差异。研究结果表明,煤种不同制得的活性焦的表面性质相差较大;炭化条件(炭化温度400—800℃、炭化时间0—60min)对最终制得的彬县煤活性焦表面化学性质影响很小。     

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 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.     

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.     

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。     

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.