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.     

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.     

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.     

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.     

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.     

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.     

Carbonization and liquid-crystal (mesophase) development. 13. Kinetic considerations of the co-carbonizations of coals with organic additives

Five coals, of rank from an anthracite to a non-caking coal, have been carbonized singly and also cocarbonized with decacyclene, mixing ratio 7:3, in the temperature range 648 K to 823 K, heating at 10 K min^?1, with various soak times. The objective of the study is to derive the basic factors which influence the kinetics of formation of mesophase and anisotropic coke. Accordingly, resultant cokes were polished and surfaces examined by reflected polarized light in an optical microscope. The size, shape and extent of anisotropic development is discussed in terms of the conditions of carbonization and the rank of coal. In these systems a somewhat larger optical texture results in cokes produced at the higher carbonization temperatures. The temperature of onset of growth of anisotropic carbon in co-carbonizations was below that of either the coal or the decacyclene. Reactivities are evidently modified. The origins, growth and coalescence of growth units of anisotropic carbon in these cocarbonizations of coals with decacyclene are demonstrated.     

Carbonization and liquid crystal (mesophase) development. 14. Co-carbonization of coals with A240 Ashland petroleum pitch: effects of conditions of carbonization upon optical textures of resultant cokes

This study examines the effect of pitch concentration, rate of heating, soak temperature and time of soak upon the optical texture of cokes prepared from the co-carbonizations of a coal (Oxcroft-Clowne, NCB Rank 802) and three vitrains of NCB Rank 204, 801, 902 with Ashland A240 petroleum pitch. Using the coal (Rank 802) with 10 wt % and 25 wt % additions of pitch caused progressive penetration of the pitch into the coal with a resultant development of a mozaic anisotropy in the coke to replace partially the original coke isotropy. With 50 wt % addition of pitch almost all of the coal particles, 600 to 1100 μm in size, were modified during carbonization. Some pitch coke was formed. For the coal and three vitrains with increasing rates of co-carbonization from 0.5–10 K min^?1 to 1200 K, using 25 wt % of A240 pitch, resultant cokes showed progressively increased extents of modification. For the two vitrains (Rank 801, 902) soaking at temperatures of 650–690 K caused a decrease in the extent of modification of isotropic coke when compared with the coke of HTT 1200 K. Evidently fast heating rates create the conditions of fluidity necessary for the pitch to modify the coal leading to growth of mesophase and anisotropic coke.     

水煤浆气化原料的成浆性研究

在实验室条件下研究了从低煤化度烟煤到高煤化度无烟煤,以及石油焦等不同气化原料煤的成浆性.为提高低煤化度烟煤的成浆浓度,在保证其混合原料灰熔融特征温度满足液态排渣前提下,将低煤化度烟煤与一种或两种煤化度较高的煤或者石油焦配比,考察了它们的成浆性.结果表明,煤化度适中的QD煤单独制浆浓度达到70%,黏度536mPa.s,流动性为A;通过不同煤种的级配,三种原料配合的料浆浓度为62%时,黏度在340mPa.s～550mPa.s之间,可以获得符合液态排渣气化要求的混合料水煤浆,扩大了气化原料来源.     

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。     

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.     

The strength of industrial cokes. 6. Further studies of the influence of coke breeze in a coal charge on tensile strength of coke

The objective of this investigation was to ascertain if there was any pattern in the dependence of the tensile strength of coke on the proportion and particle size of coke-breeze in an oven charge and to establish if it was possible to interpret the changes in tensile strength in terms of coke structural features. Using a small-scale oven in order to obtain the optimum in close control of the charge preparation and carbonization conditions, cokes were prepared from each of two coking coals blended with coke breeze. The tensile strength of these cokes was determined by the diametrical-compression test and some details of their porous nature were determined from density measurements, mercury porosimetry and optical microscopy. The results clearly demonstrate that the tensile strength of coke is, in general, systematically reduced with increasing breeze content of the oven charge, the more coarsely ground breeze leading to a greater reduction of the tensile strength at any level of breeze addition. But very finely ground breeze at relatively low levels of addition can lead to an improvement in the tensile strength. These changes correlate with variations in the apparent density and the total porosity and possibly also with the average pore size.     

Optical anisotropy of carbonized coking- and caking-coal vitrains

The purpose of this work was to characterize in detail the optical anisotropy formed during carbonization of the range of coals used in the coking industry, the ultimate objective being to attain a better understanding of the coking process. Vitrains hand-picked from a series of coking and caking coals were carbonized to various temperatures between 380 and 1000 °C. The semicokes and cokes so produced were examined by polarized-light microscopy to determine the proportions of the different types of optical anisotropy developed during carbonization. The results demonstrated that coals normally grouped within one class of the coal classification system used by the National Coal Board can lead to cokes which are significantly different in terms of their optical anisotropy. The process of the anisotropic development during carbonization can be explained generally in terms of loss of volatile matter, variations in viscosity of the plastic mass, and distortion of ordered phases by the pressure of evolving gases. Differences in carbonization behaviour as judged by the coke anisotropy can be attributed to differences in the ‘molecular-structure’ of the parent coal. In this respect the oxygen in the coal is considered to be of primary significance.     

The strength of industrial cokes. 7. Further studies of the influence of additives in a coke-oven charge on the tensile strength of coke

The objective of this investigation was to determine if the previously established dependence of the tensile strength of coke on the breeze content and particle size of coke breeze in the coke-oven charge was applicable to different types of breeze additives when used in a size range similar to that of commercial practice. Using a small-scale oven to obtain the desired close control of the charge preparation and carbonization conditions, cokes were prepared from a Yorkshire strongly-caking coal blended with either coke-oven breeze, petroleum-coke breeze, or silica sand. The tensile strength of the cokes was determined by the diametral-compression test and some details of their porous structure were obtained from density measurements and mercury pressure porosimetry. The results confirm that the tensile strength of coke varies systematically with the coke-oven breeze content of the oven charge, and in the present case, for a breeze of the particle size range used in commercial practice the tensile strength is increased at low additions and then progressively reduced at higher levels of addition. Different sources of coke-oven breeze behave in a similar manner and appear to act as an inert filler material. On the other hand petroleum-coke breeze additions progressively increase the coke tensile strength, the additive being bonded into the walls of the coke matrix. The changes in tensile strength are accompanied by systematic variations in apparent density and in porosity.     

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 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.     

无烟煤型焦反应性的研究

以无烟粉煤为主配料,分别添加ＲＳＬ和ＲＳＦ两种热塑性粘结剂。采用冷压成型高温干留制备型焦的工艺,获得几种无烟煤型焦样品,并对其进行了反应性测试。重点研究了无烟煤煤阶和粘结剂对型焦反应性的影响,为便于分析,同时对粘结剂和原料无烟煤的反应性进行了研究。研究结果表明,煤阶和粘结剂性质是影响型焦反应性的主要因素。型焦反应性随煤阶变化规律与其原料无烟煤一致,说明煤的性质可决定其型焦的反应性;另外,由两种粘结     

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.     

Carbonization and liquid-crystal (mesophase) development. 21. Replacement of low-volatile caking coal by petroleum pitch in coal blends for metallurgical coke

Cokes were prepared in a 7 kg oven from blends of high-volatile and low-volatile caking coals, using ratios of 1:1 and 3:7. To the 1:1 blend was added 7.5% of either Ashland A240 or A170 petroleum pitch or SFBP petroleum pitch 1. Micum m₃₀ and m₁₀ indices were determined on cokes from the 7 kg oven, using the $\text{1}\text{5}$ Micum drum. Optical textures were assessed using polarized light microscopy of polished surfaces of cokes. The effect of additive is to increase the strength of cokes. The pitch can be an effective replacement of low-volatile caking coal. The analysis by optical microscopy shows that with the stronger cokes from the 7 kg oven there has occurred an interaction between the coal and pitch at the interface of coal particles to produce a solution or fluid phase which carbonizes to a coke with an optical texture of fine-grained mozaics. This material could be responsible for the enhancement of coke strength, being associated with pore wall material rather than with a change in porosity. The results agree with previous work using cokes prepared in the laboratory on a small scale.     

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.