Properties and structure of metallurgical formed cokes

Properties and structure of formed cokes obtained from various raw materials using different technologies and changes of properties and structure of formed and conventional cokes occurring in the blast-furnace process were investigated. In formed cokes, in distinction from conventional cokes, there are many types of structure depending on the kind of raw materials used and on the technology of formed cokes production. Formed fuels have shown a lower degree of homogeneity and arrangement of structure in comparison with conventional cokes. In the blast furnace process a gradual arrangement of coke structure takes place. The process of structure arranging is more intensive in conventional coke. The petrographic composition of original coals has a great effect on the quality of the formed cokes. Based on the results of structural investigations, changes in the technological process can be introduced, to obtain a product of the desired quality.     

添加炭素物料改善焦炭性能的研究

通过向炼焦配煤中添加石油焦、人造石墨和天然石墨并炼焦处理，研究了添加炭素物料对焦炭性能的影响，结果发现，添加少量炭素物料有效地提高了焦炭强度并降低了焦炭的反应性。     

BJ塔板在焦化分馏塔中的应用

文章介绍了焦化分馏塔主要的特殊工艺要求。即要求所采用的塔盘具有抗焦粉和结盐沉积能力、较好的操作弹性。结合介绍了BJ浮阀的结构特点并阐述了BJ浮阀抗焦粉和抗结盐沉积及操作弹性好的机理。阐述了BJ塔板在全国各地炼油厂所取得的实际应用效果,概括性地介绍了BJ塔板在焦化分馏塔中的工业应用情况。     

Carbonization of aromatic hydrocarbons—VI: Carbonization of heterocyclic compounds catalyzed by aluminum chloride

Carbonization properties of heterocyclic compounds were studied in the presence of aluminum chloride to observe the effects of carbonization reactivity difference due to the kinds of heteroatoms and the ring structures on the structural properties of the carbon. The amount of catalyst was shown to have a significant influence on the properties of cokes. Some of the heterocyclic compounds gave graphitizable needle cokes with a suitable amount of the catalyst, some gave graphitizable mosaic cokes and the others gave non-graphitizable isotropic cokes. The tendency to give a graphitizable needle coke decreased in the order of sulfur, nitrogen and oxygen as for the heteroatom, and did in fluorene, anthracene and phenanthrene types as for the ring structure. Such a tendency is compared with that observed in carbonization under high pressure. A large part of sulfur and nitrogen atoms was left in the coke after carbonization, and no correlation was observed between the remaining amount and the structure of the coke.     

The role of liquid crystals in the formation of graphitizable carbons (cokes)

The formation of cokes and graphites proceeds via the creation from the isotropic fluid phase of carbonization of pitch and coal, of lamellar nematic liquid crystals or mesophase. This anisotropic fluid, deformable mesophase, develops as spheres within which constituent molecules are stacked parallel to an equatiorial plane. This type of structure facilitates coalescence to a coherent mass which eventually forms a graphitisable carbon. The ‘onion-skin’ structure of mesophase spheres cannot so coalesce. Different optical textures of cokes and graphites owe their origin to different chemical reactivities and fluidities of mesophase, the lower the fluidity the smaller the size of the optical texture. Mesophase from lameller molecules is compared with conventional rod-like nematic liquid crystals. Structures in needle-cokes, metallurgical coke, coke from solvent refiend coal and carbon fibre from pitch are discussed in terms of formation and properties of lamellar nematic liquid crystals.     

钢渣基高反应性焦炭气孔结构的溶损演化行为

在工业配合煤中添加1%钢渣制备高反应性焦炭,采用低温氮气吸附法分析高反应性焦炭（HRC）和普通焦炭（BC）在1100℃下溶损不同比率碳素（5%~50%）后焦炭的气孔结构,并结合分形理论研究焦炭溶损反应过程中孔结构的演化特性。结果表明,随着碳素的溶损,HRC的吸脱附曲线的变化幅度比BC的大,吸附等温线由Ⅰ型向Ⅱ型的转变较晚;焦炭的比表面积和微孔孔容随碳素的溶损先增大后减小、总孔容逐渐增大,而HRC的比表面积增率（ΔS _BET /Δx）比BC的大,孔径分布也相对较宽;HRC的分形维数D ₁和D ₂随碳素溶损而变化趋势与BC的有较大差异。这说明高反应性焦炭中的钢渣通过增加了焦炭表面上活性点影响焦炭溶损过程中气孔结构的演化行为。     

Comparative study of reactivity to CO2 of cokes used in stone wool production

The reactivity towards CO₂ of seven types of commercial coke used in stone wool production has been measured in a thermo gravimetric analyser (TGA). The cokes originated from Western and Eastern Europe and from China. For three of the cokes, the porosity, density and surface area were determined. The directly measured porosities of the cokes was slightly low, indicating that there are pores that are not connected with the outer surface. This is supported by the measured densities and microphotos.The measurements showed that the Chinese cokes were the least reactive while the European cokes made on American coal were the most reactive. The reactivity of the one Eastern European coke in the measurements had an intermediate reactivity.Simulations with a cupola model show that 25% more coke is needed for stone wool production if the coke is changed to a type with half the reactivity towards O₂ and CO₂.The TGA method proved to be a good method for ranking the coke with respect to reactivity with CO₂.     

Interaction between a coke and a tar. 2. Limit of tar penetration in coke porosity

The limit of penetration of a given coal-tar pitch into two cokes during mixing of the coke and liquid tar has been studied. It was shown that tar penetration is limited by compression of gas occluded in pores. Mercury porosimetry of cokes and pyrolysed coke-tar mixtures as well as micrographs of cokes impregnated with tar allow one to estimate the limiting pore diameter of tar penetration into coke at ca. 6 μm for the system considered.     

Investigation of the structural forms of potassium in coke by electron microscopy and X-ray absorption spectroscopy

An investigation of the chemical and structural forms of potassium in coal, coke, and potassium-enriched coke has been made. The principal analytical techniques used were X-ray absorption spectroscopy, computer controlled scanning electron microscopy, and scanning transmission electron microscopy. The potassium in the bituminous coals investigated was contained in the clay mineral illite, which was transformed to a predominantly amorphous or glassy potassium aluminosilicate during coking at temperatures of 1050–1100 °C. In cokes artificially enriched in potassium and annealed at 1260 °C under argon, two principal forms of potassium were identified: potassium in K-enriched aluminosilicates and silicates, and potassium dispersed throughout the carbonized macerals and bonded to carbon. Although the aluminosilicates and quartz act as effective potassium receptors, approximately half of the added potassium was dispersed through and bonded to the carbonized macerals. Both potassium forms were predominantly amorphous in structure. Analysis of the electronic structure and local atomic environment by X-ray absorption spectroscopy showed that these amorphous phases exhibited some similarities to chemically similar crystalline phases such as leucite (KAlSi₂O₆) and intercalated potassium-graphite (KC₈). X-ray absorption spectroscopy measurements on samples extracted from a blast furnace experiencing high alkali levels indicated that the forms of potassium in the blast-furnace coke were qualitatively similar to those in the laboratory prepared cokes, and suggested a possible mechanism for alkali attack on refractories.     

Carbonization of pitch: Compatibility of components in carbonization

The carbonization of four kinds of solvent-refined-coal (SRC) pitches was investigated in order to determine the properties required for the formation of needle coke. Although the pitches were free from Ql materials, two of them gave needle cokes, whereas the other two gave mosaic cokes. The BS fractions of all pitches formed needle cokes, and all Bl fractions were infusible and isotropic. A combination of suitable BS and Bl fractions gave a needle coke, whereas another mixture formed a mosaic coke, indicating that the BS and the Bl fractions can be compatible to yield a needle coke. Cocarbonization of the BS fractions from other pitch sources with the Bl from the SRC pitches was further studied to evaluate the compatibility, which has been discussed from the structural viewpoint. Trials to improve the properties were proposed, based on the structural information.     

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.     

Carbonization and liquid-crystal (mesophase) development. 18. carbonization of coal-extract solutions (non-hydrogenated): influence of digestion conditions upon optical texture of cokes

Coal-extract solutions have been produced by the dissolution of a prime coking coal in anthracene oil followed by the removal of the undissolved solids. A range of coal-extract solutions prepared under different conditions was carbonized and the optical texture of the polished surfaces of the resultant cokes were assessed. The coal-extract solution prepared with the longest digestion time and at the highest temperature produced a coke with the largest anisotropic domains with some flow structure. Removal of the anthracene oil component of the coal-extract solution by extraction with selected solvents modified the carbonization behaviour such that although the coke yield increased substantially there was a significant decrease in the size of the anisotropic domains of the resultant cokes.     

Carbonization and liquid-crystal (mesophase) development. 16. Carbonizations of soluble and insoluble fractions of coal-extract solution

A coal-extract solution prepared by extraction of a coking coal (CRC 301a) with anthracene oil by the National Coal Board is separated into fractions using solvents of increasing solvent power. These fractions are carbonized to 823 K and the optical textures of resultant cokes are assessed. The objective of the study is to examine the role of the molecular components of the coal-extract solution including the residual anthracene oil in mechanisms of formation of the optical texture of the anisotropic coke. Generally, the low-molecular-weight fractions of the coal-extract solution produce cokes with larger sized optical textures than the coke from the parent coal-extract solution. The higher-molecular-weight fractions produce cokes with smaller sized optical textures. Isotropic coke is produced from material which is not soluble in benzene and tetrahydrofuran. Within this parent-coal-extract solution it would appear that the dominant partner effect is influential over the size of the optical texture of coke from the coal-extraction solution, that is the minor component of smaller molecules controls the necessary growth of liquid crystals. Also, the presence of anthracene oil augments the size of optical texture of resultant cokes by providing the necessary physical fluidity of the system and possibly some chemical stability.     

Devolatilisation behaviour of petroleum coke under pulverised fuel combustion conditions

The combustion of petroleum coke in large scale facilities has been limited due to its high sulphur content, but the increasing installation of flue-gas desulphurisation units makes possible the firing of petroleum coke either as a primary fuel or blended with coals. This study focuses on the behaviour of three fuel-grade petroleum cokes of different provenance under pulverised fuel combustion conditions. These cokes, ground and sieved 125–20 μm were fed to a drop tube reactor operating at 1300 °C under different atmospheres to produce chars with different combustion degrees. Char reactivity assessment was performed isothermally in a thermobalance at 550 °C and morphology and optical texture of the chars were studied by optical and scanning electron microscopy. Petroleum coke chars are composed of two main types of particles: (i) porous anisotropic particles that passed through a plastic stage and generated either cenospheric or network-like chars and (ii) angular particles with fine-mosaic optical texture that did not swell and show abundant contraction cleats. The relative proportions of both types of particles were very different in the three petroleum coke chars indicating significant differences in their devolatilisation patterns. The morphology and optical texture of the petroleum coke chars were related to their reactivity (as measured in a thermobalance) and to the characteristics (chemical composition and optical texture) of the parent petroleum cokes, in an attempt to understand the implications of their different devolatilisation behaviours on the combustion efficiency.     

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 semi-industrial scale study of petroleum coke as an additive in cokemaking

The addition of petroleum coke to a typical industrial coal blend used in the production of metallurgical coke was studied. Cokes were produced at semi-industrial scale at the INCAR coking plant, using petroleum coke of different particle size distribution as an additive. Special attention was paid to changes caused in the textural properties (porosity, pore size distribution, fissures at the interface between metallurgical coke and petroleum coke) which have been found to be responsible for variations in the metallurgical coke quality parameters (e.g., mechanical strength and reactivity towards CO₂). Variation in porosity was found to depend on particle size and the proportion of the additive. The decrease in the microporosity (i.e., pore radius<3.7 nm) of the metallurgical cokes observed when petroleum coke is added to the coal blend, is postulated to be one of the main factors responsible for the decrease in the reactivity of these cokes. The variation of the mechanical strength indices can be explained by the changes in porosity and the quality of the interfaces between petroleum coke and metallurgical coke.     

Formation of coke during thermal hydrocracking of Athabasca bitumen

The formation of two structurally different cokes during thermal hydrocracking of Athabasca bitumen is attributed to differences in coking properties of the asphaltenes and the deasphalted heavy oils. The grain-mosaic coke structure formed from the asphaltenes may be ascribed to the presence of crosslinkage groups derived from the phenolic character of this fraction of the bitumen. Carbonization of the deasphalted heavy oils of the bitumen results in a flow-type coke structure. These two cokes appear to form independently of each other and can therefore be readily identified in samples collected from the reactor.     

Oil sands cokes affect microbial activities

The upgrading of bitumen extracted from oil sands in Alberta, Canada is producing vast quantities of coke that must be stored in a manner that will not harm the environment. It has been assumed that these cokes are inert, and therefore should not affect any biological processes. Coke samples were incubated in two microbiological tests to determine if they are inert. One was a methanogenic bioassay, which showed that higher coke dosages led to lower methanogenic activity. In the second test, coke was incubated with heterotrophic, aerobic bacteria that are known to extract organic sulfur from coal yielding sulfate in the medium. Sulfate production was observed with one of the coke samples. Thus, the cokes are not inert.     

Optical properties of vitrinite carbonized at different pressures

The effect of pressure on the optical properties of cokes from a medium volatile bituminous coal (carbon = 87.9 wt% daf), some carbonized at atmospheric pressure and others under hydraulic pressure (21–310 MPa), over temperatures ranging from 350 to 600 °C at 50 °C intervals, has been studied. The cokes formed at atmospheric pressure developed fine grained mosaics, while medium-flow type mosaics formed in coke carbonized under hydraulic pressure. The thermal decomposition stage began at lower temperatures with increasing hydraulic pressure, resulting in a prolonged devolatilization phase for coke formed at a pressure of 21 MPa. Hence the fluidity of samples carbonized under pressure decreases with increasing hydraulic pressure. Pressure promotes the optical anisotropy apparent from the level of bireflectance. The reflectance of coke formed at atmospheric pressure is higher than that of cokes carbonized under hydraulic pressure, perhaps due to the inhibitory effect of entrapped volatile matter during carbonization under hydraulic pressure. The morphological features of vitirinite carbonized under pressure resemble those of coals naturally affected by heat.     

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.