Influence of the quinoline-insoluble matter in pitch on carbonization behaviour and structure of pitch coke

The influence of the quinoline-insoluble matter in pitch on the carbonization behaviour and especially on the pitch-coke properties is of basic interest both for the production of pitch coke and the manufacture of carbon electrodes. A more isotropic coke is produced by increasing the amount of quinoline-insolubles. The coefficient of thermal expansion (CTE) by volume measured directly at the coke particle is strongly influenced by the type of quinoline-insoluble. A larger amount of the primary type of quinoline-insolubles causes a large increase of the CTE (volume) from 3.2 to 17.4 × 10^?6K^?1, whereas the secondary type influences the CTE only slightly. This strong influence of quinoline-insolubles on the structure of pitch-binder coke results in a remarkable increase of mechanical strength of carbon artefacts.     

Influence of the coke filler on the carcinogenicity of pitch–coke mixtures on carbonization

The emissions of benzo[a]pyrene at different temperatures and its concentration in the exhaust gases are measured in laboratory experiments on the carbonization (at temperatures up to 850°C) of coalpitch and petroleum-pitch binders and their mixtures with roasted petroleum and pitch coke. These pitch–coke mixtures are similar in composition to the anode mass used in aluminum production. The experiments confirm that the total benzo[a]pyrene emissions are much greater in the carbonization of petroleum pitch produced by cracking (T _so = 100°C) than for electrode pitch (T _so = 89°C) and other coal pitch. In most experiments, the benzo[a]pyrene emissions in the carbonization of pitch–coke mixtures is markedly less than for individual binder pitches. It is found that the benzo[a]pyrene emissions in the carbonization of a mixture based on pitch coke are much less than for a mixture based on petroleum coke in the high-temperature region that presents the greatest environmental hazard.     

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.     

Structure and carbonization properties of pitches produced catalytically from aromatic hydrocarbons with

Carbonization properties of pitches synthesized from some aromatic hydrocarbons by the aid of were studied under atmospheric 1.1 and 3.1 MPa pressures. The highest coke yields obtained under atmospheric pressure and 3.1 MPa were 64% and 85%, respectively, both of which were observed with anthracene pitch. Pyrene pitch exhibited a low coke yield of 37% under atmospheric pressure, but as high as 85% under 3.1 MPa.The pitches were revealed with ¹H-NMR and FD-MS to consist essentially of oligomers of starting aromatic rings such as dimers, trimers, and tetramers. The oligomers carried significant amounts of naphthenic hydrogens, which provide their low softening point and enable the development of an anisotropic flow texture when the pitch was carbonized. The carbonization scheme is discussed in relation to the coke yield.     

Carbonization of coal pitch with additives

The ability of organic and inorganic additives (polyethylene terephthalate, titanium dioxide, finely disperse carbon, petroleum bitumen) to reduce the carcinogenic impact of coal-pitch carbonization is studied. Additives may reduce the quantity of pitch sublimates and their content of carcinogenic polycyclic aromatic hydrocarbons. Some additives are able to reduce the benz[a]pyrene content in the exhaust gases, but its complete elimination is impossible, since benz[a]pyrene is a natural product of the high-temperature pyrolysis of organic materials. For this reason, additions of petroleum products to coal pitch cannot reduce the benz[a]pyrene emissions in the exhaust gases.     

Carbonization of coal-tar pitches: effect of rank of parent coal

The object of the present work was to investigate whether the rank of coal from which the coal-tar pitches were obtained had any bearing on their carbonization behaviour. Using six laboratory produced pitches it is shown that the behaviour during the mesophase temperature range, and consequently the size of the anisotropic flow structures in the pitch coke, vary with the rank of the parent coal.     

Characteristics and carbonization behaviors of coal extracts

N-methyl pyrrolidone (NMP) raw coal extract (EXT), hydrogenated coal extract (HEXT) and the blend of EXT and HEXT in NMP (BLD), from two bituminous coals, were studied. The extracts were carbonized in both tube-bomb and a temperature programmable furnace. Elemental analysis, FTIR spectroscopy and optical microscopy techniques were employed to characterize the extracts and the carbonization residues. It was found that the extracts resembled petroleum-derived pitches in the hydrogen content and (C/H)_atomic ratio. Higher oxygen and nitrogen contents differentiated the coal extracts from commercial petroleum pitch. More carbon and hydrogen, and lesser oxygen and sulfur differentiated HEXT from EXT. The ratios of integrated IR band intensity for aromatic and aliphatic CH stretching indicate that the relative content of aliphatic hydrogen in EXT is higher than in HEXT. HEXT contains comparatively more aromatic hydrogen, a feature necessary for thermal stability and fluidity during carbonization. BLD materials are at a place somewhere in between. Kinetic modeling of the aliphatic hydrogen change during carbonization reveals that EXT has high carbonization rate and low apparent activation energy. This can be related to the optical texture size of carbonization residues. The residues made from EXTs exhibited fine mosaic optical texture and limited mesophase development. HEXTs were readily converted into highly anisotropic coke. BLDs produced carbonization residues with intermediate properties. Extracts with similar activation energies produced similar residues in the same coal series. The degree or extent of anisotropy displayed by the carbonization residues was found to be dependent on the relative distribution of aromatic and aliphatic hydrogen.     

Rheological characteristics of coal tar and petroleum pitches with and without additives

An extensive study of rheological characteristics of coal tar and petroleum pitches with and without additives, namely, petroleum coke, natural graphite and carbon black has been made. It is found that all pitches, pure or mixed with a carbon additive are not Newtonian as reported in the literature, but behave Theologically as Bingham plastics with certain yield stress and plastic viscosity at all temperatures of measurement between 85–180°C. The yield stress and plastic viscosity both decrease with increase in temperature of the pitch. A pure petroleum pitch having the same softening point as that of a coal tar pitch is found to have a lower viscosity compared to that of the latter at all temperatures of measurement. This suggests that the criterion of softening point as a measure of suitability of a coal tar pitch binder in the manufacture of artificial carbon is not sufficient for petroleum pitches. Addition of ten parts of carbon black by weight of pitch results in a considerable decrease in viscosity change with temperature of the coal tar pitch compared to almost insignificant change in the case of the petroleum pitch of the same softening point. However, the addition of petroleum coke or natural graphite makes the pitch more viscous but does not change the temperature dependence of viscosity of either of the two types of pitches. The implications are discussed.     

Carbonization of hydrogenated ethylene tar pitch; study of the pitch molecular compactness factor and coke optical texture

Compactness factors of aromatic molecules in hydrogenated ethylene tar pitch were calculated as a parameter to relate to properties of mesophase of the carbonization system. Compactness factors, φ, derived from structural analyses of hydrogenated ethylene tar pitch were also related to the size and shape of optical textures of resultant cokes. Hydrogenated ethylene tar pitches having values of φ 〉 0.5 gave cokes with flow type anisotropy and relate to formation of peri-condensed structures. The spin-lattice relaxation times, T₁, for the cokes derived from hydrogenated ethylene tar pitch, are related to their optical texture.     

Carbonization of coal pitch with graphite additives

The influence of added pyrolytic graphite and graphite foam on the crystalline structure of the product formed in the carbonization of moderate-temperature coal pitch at 900°C is investigated by X-ray diffraction analysis. All the additives catalyze the formation of graphite structures in pitch carbonization. However, no direct dependence of the catalytic efficiency on the structure of the carbon additive or its specific surface is observed. In the presence of graphite additives with a specific surface of 4–12 m²/g, more than 20% of a crystalline fraction is formed in the carbonization of pitch. This fraction is highly ordered, with large crystallites. On adding graphite foam, with a high specific surface (110 m²/g) and low packing density (4 g/L), the formation of graphite structures on pitch carbonization is less effective.     

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.     

沥青粘结剂产炭率对制品性能的影响

研究了粘结剂沥青产炭率与块状炭制品材料性能的关系,拟通过提高粘结剂沥青产炭率的方法改善炭制品的性质。实验采用比目前工业沥青粘结剂产炭率更高的沥青作为粘结剂,经过混捏、成型和焙烧制成炭制品。研究发现,采用产炭率高的粘结剂可以得到性能较好的产品,但对于强度来说,过高产炭率的粘结剂并不总是正面影响的,应考虑到粘结剂中β组分的含量。     

Molten storage and carbonization characteristics of premium grade coal-tar pitch: Influence of crude tar type and distillation conditions

A growing trend towards the transport and use of molten rather than solidified pitch has caused tar distillers to examine the relative stability of pitches while held in storage tanks. The scope of laboratory storage-stability tests can be extended to higher temperatures as a method of studying the earliest stages of pitch polymerization/carbonization. Some indications of the ultimate performance of the pitch in the end-use process can be gained. Crude tar has a strong influence on the ultimate properties and performance of a pitch. Seven tars have been made into 120 °C Mettler softening-point pitches by two distillation methods to study their subsequent storage and carbonization behaviour. The behaviour exhibited by each pitch allows a judgement on overall ‘reactivity’ and on the sensitivity to thermal conditions in the distillation of each tar. Two distillation schemes were adopted: batch distillation followed by heat treatment; and batch distillation at a pressure which was progressively reduced. The results show that time at elevated temperature has a major effect on the properties and performance of the resulting pitch. Vacuum distillation allows lower processing temperatures. Larger amounts of secondary quinoline-insolubles were formed under the ‘distillation with heat treatment’ scheme. Complete wetting of coke by pitch took place at lower temperatures for the vacuum-distilled pitches. Heat-treated pitches increased more rapidly in softening point and lost more mass when thermally soaked. Distillation under vacuum conditions resulted in significantly modified pitch carbonization characteristics.     

Chemistry of pitch carbonization

The conversion of pitch to carbon is a complex process encompassing a multitude of physical and chemical transformations among the many pitch components. Studies on both individual aromatic compounds and pitches have shown that polymerization through loss of side chains and hydrogen is the main chemical reaction. Molecular rearrangements are also prevalent. A continual increase in molecular weight through polymerization and loss of low molecular weight volatiles results in the transformation of pitch to mesophase, coke and ultimately carbon. Stable free-radicals are formed during both the polymerization and rearrangement processes. These various aspects are reviewed to develop a general mechanistic sequence for pitch carbonization.     

KOH activation of pitch-derived carbonaceous materials—Effect of carbonization degree

Two series of mesophase pitches and semi-cokes of different carbonization degree were produced by heat treatment of anthracene oil derived pitches P1 and P4 in the temperature range of 460-700 °C. These carbonaceous materials were activated with potassium hydroxide at 700 °C using 1:3 reagents ratio to assess the effects of the precursor optical texture and carbonization degree on the activation behavior. The results show that the increase in the pitch pretreatment temperature suppresses propensity to the pore generation while enhancing particle breaking. The effect can be illustrated by decreases in the BET surface area S_BET from ~ 2700 to ~ 1500 m² g⁻¹ and the micropore volume V_DR from ~ 0.85 to ~ 0.45 cm³ g⁻¹. These parameters are inversely related with the H/C atomic ratio of precursor. In contrast, the anisotropic development of pitch coke, varying from flow type to mosaics, has a slight effect on the activation behaviour. The mechanism of porosity generation, that is proposed, stresses the role of hydrogen occurring at the edges of graphene layers and potassium metal insertion/deinsertion on the porosity development and particle disintegration during KOH activation of pitch-derived carbons.     

Carbonization behaviour of pitch in the presence of inert material

The influence of silica gel (< 45 μm) as an inert additive on the carbonization reactions of A240 pitch was investigated by optical microscopy, measurements of transferable hydrogen, high-temperature e.s.r. and high-temperature ¹H n.m.r. Additions of silica gel have the effect of reducing the size of the optical texture of mesophase which appears in the early stages of carbonization. The higher the concentration of silica gel, the smaller is the amount of transferable hydrogen. The spin concentration of pitch increases with increasing silica gel content. Measured values of $\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, using high-temperature ¹H n.m.r., suggest that the molecular motions in the pitch become restricted on addition of silica gel. The effect of silica gel on the physical properties and chemical reactivity of carbonizing pitch is discussed.     

Carbonization and liquid-crystal (mesophase) development. 20. Co-carbonization of a high-volatile caking coal with several petroleum pitches

A high-volatile caking coal and five petroleum pitches were carbonized singly and coal/pitch systems were co-carbonized to 1273 K in the ratio of 75 wt% coal and 25 wt% pitch. Optical textures of cokes from the single carbonizations and co-carbonizations are assessed in terms of modification to the coalcoke by the pitch and unmodified pitch-coke using a point-counting technique. The pitches differ considerably in their carbonization behaviour. Each pitch can be placed into one of three groups defined in terms of their interaction with the high-volatile caking coal. A passive pitch does not modify the coalcoke but apparently carbonizes independently of the coal. An active pitch modifies some of the coalcoke. No pitch-coke can be detected. A super-active pitch modifies the coal-coke extensively beyond the extent expected from a 25% addition. No pitch-coke can be detected. The effects are related to the ability of the pitch to cause depolymerization of the coal. Quinoline-insoluble material in pitch may inhibit modification.     

Étude des phénomènes de mouillabilité du carbone par le brai liquide

One of the processes used in the manufacture of carbon/carbon composites makes use of impregnation with pitch of a multidirectional structure of carbon rods made of carbon fibres at high temperature followed by carbonization under high pressure. A densification of the composite is obtained by repeated impregnations.Since the mechanical properties of the composites must likely depend on the quality of the interface formed between the carbon rod and the liquid pitch matrix, the wetting properties of pitches of various origins and properties (Table 1) were studied for several carbon rods (Table 2). A tensiometric method based on the weight of pitch lifted during immersion of the carbon rod at 350°C was used (Fig. 1).Measurements of the surface energy of the pitches in the liquid state at 350°C (Table 3) and in the solid state at room temperature (Table 4) show that the surface energy is practically independent of the origin of the pitch and that the surface polarity of the pitch is negligible. On the contrary, the values of the contact angle at 350°C is higher for the petroleum pitch No. 1 than for the coal tar pitches (Table 5).The wettability criteria, i.e. the spreading coefficient S and the wetting tension τ, derived from the measured surface energy and contact angle, confirm the lower wetting ability of the petroleum pitch (Fig. 2). These criteria may explain why the densification process (number of impregnations and carbonization cycles necessary to reach an apparent density of the composite of 1.90) is much more difficult with petroleum pitch. On the contrary, the adhesion criterion factor, expressed as the reversible energy of adhesion between the liquid and the solid at 350°C, has the same value whatever the origin of the pitch. Since the degree of adhesion might influence the quality of the carbon/carbon interface in the composite, the same value of the adhesion criterion factor may explain why all composites, at equivalent density, show about the same compression and torsion strengths.The difference between the wettability and adhesion for the pitches of different origins is due to the difference in the spreading pressure π; this quantity measures the decrease of the surface energy of the carbon rod resulting from the adsorption of the pitch vapor. The calculations reveal that, whatever the surface energy of the carbon rod, the petroleum pitch leads to a larger reduction of the surface energy of the solid than the coal tar pitches (Fig. 3).The wettability and adhesion criteria adopted in this study seem to (at least to a first approximation) explain the dependence of the mechanical properties of the carbon/carbon composites on the type of pitch and on the processing conditions.     

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.     

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.