Carbonization and liquid-crystal (mesophase) development. 17. Co-carbonization of a solvent-refined coal with petroleum pitches and hydrogenated coal-extract solution

This study characterizes the optical textures of cokes prepared by the carbonization of Ashland petroleum pitches, of non-hydrogenated and hydrogenated coal-extract solutions (CES) and of blends of non-hydrogenated CES materials with the petroleum pitches and hydrogenated CES materials. At an HTT of 823 K petroleum pitches produce cokes with large sized optical texture of flow-type anisotropy characteristic of needle-cokes. The non-hydrogenated CES materials produce cokes with optical textures of mozaics, 2–10 μm. However, following hydrogenation the CES materials carbonized to cokes all of which possess considerable large sized optical textures which for some materials resemble that of needle-cokes by possessing strong flow-type anisotropy, > 100 μm. Hydrogenation of the CES materials evidently facilitates the physical and chemical requirements for growth and coalescence of lamellar nematic liquid-crystals and mesophase from the fluid phase of carbonization leading to anisotropic carbon. Co-carbonizations of the non-hydrogenated and hydrogenated CES materials exhibit the dominant partner effect and are comparable in behaviour with Ashland petroleum pitches which are known to produce needle-cokes on carbonization.     

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.     

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.     

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.     

Co-carbonization of hard coals and coal extracts 1. The co-carbonization of low rank coals with extracts

Studies on the influence of an additive derived from coal on the coking properties of lower-rank coals and on the structure of cokes obtained from blends have been undertaken in our laboratory since 1978. The two coal extracts from flame coal (Int. Class. 900) and gas-coking coal (Int. Class. 632) were used as additives. The results indicate that the blends prepared from low-rank coals — flame coal (Int. Class. 900), gas-flame coal (Int. Class. 721) and the extracts possess better coking properties in comparison to the parent coals. The optical texture and the degree of structure ordering of the cokes obtained from blends is related to the amount of extract in the blend. With increasing extract content in the blend, increases were observed in the amount of optically anisotropic areas in cokes from low-rank coal/extract blends and the crystallite height (L_c) of cokes from the blends. The isotropic optical texture of cokes from low-rank coals can be modified by coal extracts to an anisotropic optical texture. The non-fusible coal is the most difficult to modify. An explanation of the observed phenomena is given.     

Carbonizations under pressure of chloroformsoluble material of coking vitrinite

Chloroform-soluble material from a Polish coking coal was prepared by extracting the coal after heating it initially to 673 K for 15 min. The soluble material was carbonized in sealed gold tubes to 800 K and 873 K at 200 MPa pressure and to 800 K, 1000 K and 1200 K at atmospheric pressure. Coke morphology was assessed by SEM with optical texture (micro-texture) being assessed by polarizedlight microscopy of polished surfaces. Cokes from the pressure carbonizations (100 wt % yield) showed coalescing spherule morphology, 10 to 20 μm diameter, and are totally anisotropic. The material normally lost as volatiles thus contributes totally to the formation of mesophase and anisotropic coke. Coke from the carbonization of the soluble material at one atmospheric pressure (41 wt % yield) is composed mainly of anisotropic fine-grained mozaics in the range 1–5 μm. Carbonization under pressure extends the range of sizes of optical texture in cokes from this chloroform-soluble material. Applications may exist in graphite manufacture.     

Unusual structures in mesophase from a petroleum pitch

Cokes from the carbonization of a petroleum pitch possess an optical texture containing anisotropic spherules with an unusual structure. These spherules (10 to 20 μm diameter) were found to be present in the original pitch and could be removed as a quinoline-insoluble fraction. This suggests that the spherules are formed during the modification of the pitch after initial fractionation of the petroleum feed-stock. The optical texture of these spherules, examined by polarized light optical microscopy, reveals a complicated ‘rosette’ structure quite unlike the structure of the spheres of mesophase now known as ‘Brooks and Taylor’ spheres. An EDAX analysis of polished segments of the spherules indicated no unusually high concentration of inorganic matter, e.g. vanadium, suggesting that the spherules did not originate from asphaltenes. The influence of such spherules or inclusions in the parent pitch upon properties of resultant cokes is briefly commented upon.     

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.     

Structure in metallurgical cokes and carbons as studied by etching with atomic oxygen and chromic acid

Anisotropie carbons and cokes exhibit an optical texture or micro-texture in the size range 0.5–300 μm in polished surfaces using optical microscopy. Structure within this optical texture can be studied as the topography created by etching surfaces with atomic oxygen and chromic acid. Atomic oxygen preferentially etches an isotropic carbon layer which exists between the grains of the fine-grained mozaics. Chromic acid oxidizes or etches selectively the surfaces of anisotropic carbon to create fissures parallel to basal plane orientation. Structural components within petroleum cokes, carbon fibres and carbon/carbon fibre composites are revealed. Chromic acid oxidizes isotropic components in metallurgi-cal cokes more slowly and so reveals the structure of cokes as prepared from co-carbonizations of coal with petroleum pitch. It is considered that these etching techniques augment our knowledge of internal structure within carbons and cokes and of considerations of strength and fracture in these materials.     

Composition of pore-wall material in metal-lurgical coke: Considerations of strength,gasification and thermal stress

The optical texture of metallurgical cokes consists of anisotropic carbon made up of mozaics, 0.5–10 μm in size of flow-type anisotropy, 10–60 μm in size, as well as inert and isotropic material. Cokes from different coal sources possess optical textures which are different, being composed of different extents of the above components. The study examines the optical texture of polished surfaces of cokes and relates changes in surface topography caused by gasification by carbon dioxide at 1173 K, by heat treatment to 2073 k and by etching with atomic oxygen at 293 k to the optical texture. The results support a model to explain the strength of coke and its resistance to breakage caused by gasification, mechanical and thermal stresses, in terms of the size, orientation and bonding of the varied components which constitute the composite structure of coke material.     

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.     

Structure of the cokes obtained from the group components separated from coking coal vitrites by selective thermosolvolysis

The examination of the structure of cokes obtained from extracts separated from preheated vitrites of coking coals by progressive and continuous extraction with chloroform was carried out. The structural ordering (interplanar spacing and crystallite dimensions) of the cokes depends on the rank of the parent vitrites but it does not depend on the degree of extraction. The occurrence of optical anisotropy in cokes from the extracts is connected with both the rank of the parent vitrite and the degree of extraction. In the formation of the optical anisotropic structure during the carbonization of coking coal vitrites, the part of the extract which is of small size, which partially undergoes decomposition, is an important factor.     

Carbonization and liquid-crystal (mesophase) development. 9. The co-carbonization of vitrains with Ashland A200 petroleum pitch

Vitrains from a wide range of ranks of coals were carbonized singly and also co-carbonized (HTT 1273 K) with 25% of Ashland A200 petroleum pitch. Polished surfaces of the resultant cokes were examined for optical texture in a polarizing-light optical microscope using a half-wave retarder plate to produce interference colours. For the anthracites, there is no modification of either component during co-carbonization. The growth of optical texture from the A200 pitch is not affected. For all caking vitrains the optical texture of coke from the blend system is extensively modified when compared to the optical texture of coke from the vitrain. For the low-rank non-caking vitrains the isotropic coke becomes totally or partially anisotropic in co-carbonization. The mechanism of modification of the optical texture of resultant cokes is related to the formation of nematic liquid crystals, mesophase and the semi-coke. It is not considered that the chemistry of pyrolysis is modified on cocarbonization of the vitrain and pitch.     

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.     

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. 8. The co-carbonization of coals with acenaphthylene and decacyclene

Several coals of different rank have been carbonized singly and also co-carbonized with acenaphthylene and decacyclene. The resultant cokes were mounted in resin and polished surfaces were examined for optical texture using a polarized-light optical microscope fitted with a half-wave retarder plate. The optical texture can be assessed qualitatively (visually) or quantitatively by a point-counting technique in terms of size and shape of constituent isochromatic anisotropic units. Some cokes from coals were Isotropic. Acenaphthylene was only able to exert a smaller influence than decacyclene on the optical texture of the resultant cokes from co-carbonizations. Decacyclene was able to modify the optical texture for both the low-rank non-fusible and the caking coals. The effects of changing the proportions of coal to additive were examined. Results are interpreted in terms of ‘depolymerization’ of the coal by the action of the additive (as solvent) and also by the action of the additive in modifying the processes of formation of semi-coke via nematic liquid crystals.     

催化裂化油浆组成分布对中间相沥青光学织构的影响

以SLO-LH、SLO-SH和SLO-YN催化裂化油浆为原料,利用热缩聚法制备中间相沥青,系统分析了油浆的烃组成分布、沸点分布以及核磁结构特征,关联了中间相沥青光学织构与原料性质组成关系。结果表明,SLO-SH和SLO-YN油浆中的分子量和组成分布较窄,在给定反应条件(430℃、0.7 MPa)下制备中间相沥青的光学织构指数(OTI)值分别为45和50,中间相织构主要由大面积的域及流域组成,镶嵌结构较少。相对于SLO-SH与SLO-YN,SLO-LH样品的烃组成与沸点分布明显疏散,得到的中间相主要由镶嵌组织与小域构成。结果表明集中分布且芳烃含量高有利于得到高收率与高OTI值的优质中间相沥青,对油浆组分进行分离是制备高品质中间相沥青和针状焦的必要途径。     

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.     

The role of low-molecular-weight components in the pyrolysis of pitches

Two pitches of different volatile contents, obtained from the same coal tar by different procedures, were characterized by elemental analysis, solubility, ¹H n.m.r., donor—acceptor ability, FT-i.r., extrography and size-exclusion chromatography. Their pyrolysis behaviour was followed by hot-stage microscopy and thermogravimetric analysis. The pitches were carbonized in a horizontal furnace and the resulting cokes were characterized by optical microscopy. Three partly devolatilized pitches were prepared by thermal treatment of the two pitches and their pyrolysis behaviour was compared in terms of mesophase development and optical texture of coke. The results indicate a significant influence of low-molecular-weight components of pitch on the development of mesophase but no effect on the subsequent optical texture of the coke.