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.     

Release of carcinogenic hydrocarbons in the carbonization of coal pitch

The carbonization of industrial coal-pitch samples is studied, with particular attention to the liberation and conversion of benz[a]pyrene and other carcinogenic polycyclic aromatic hydrocarbons. The hydrocarbon composition of pitch sublimates and the benz[a]pyrene concentration in the smokestack gases are determined during regular and high-speed carbonization. The maximum benz[a]pyrene content in the smokestack gases is seen at 750–800°C, regardless of its content in the initial pitch. The benz[a]pyrene content basically determines the carcinogenic hazards of pitch processing.     

Carbonization of pitches in geometrically restricted spaces. Application to granular carbon–carbon composites

During granular carbon–carbon composites manufacturing, the binder (a pitch) is carbonized while surrounded by solid filler particles. This geometrical limitation imposed on the carbonization medium results in constraints responsible for textural modifications of the pitch-based coke. We studied the consequences of geometrical limitation on pitch carbonization, and also the influence of the as-formed composites multiscale organization on their mechanical properties and carboxyreactivity behavior. The micrometer scale is relevant to understand composite reactivity while the submillimeter scale enables a better comprehension of the mechanical properties.     

Effect of densification parameters on the low-energy tribological behavior of carbon/carbon composites

The low-energy tribological behavior was investigated in carbon/carbon composites fabricated by processing with different densification parameters. In the densification process, different impregnating precursors and carbonization temperatures were used to investigate the influence on physical and mechanical properties, microstructure and tribological behavior. Experimental results indicate that the density and hardness of resin-based specimens are higher than those of pitch-based specimens after four densification cycles. When increasing carbonization temperature in the specimens based on coal tar pitch, the open porosity increases whereas both the bulk density and the hardness decrease. When comparing the tribological properties of the specimens with different impregnating precursors, coal tar pitch specimens show lower and more stable friction coefficients and exhibit lower weight losses. This is because the pitch matrix is transferred to the preferred orientation structure carbon after carbonization. The different carbonization temperatures do influence the tribological properties; specimens carbonized at 700 °C exhibit the lowest weight loss and the most stable friction coefficient.     

Carbonization of pitch

An overview is presented of the many factors which influence the process of carbonization of pitch and hence the properties of pitch cokes. The controlling factors include type of starting material, the industrial process of carbonization, the role of quinoline-insoluble material and carbonization conditions. Several coke parameters are studied and related to the carbonization process by multiple regression analysis. Kinetic data are presented together with a schematic model of coke formation.     

Influence of oxidative stabilization on the electrochemical behaviour of coal tar pitch derived carbons in lithium batteries

A commercial coal tar pitch was thermally treated at 430 °C for 4 h and then submitted to hot filtration in order to separate the isotropic phase from the mesophase developed during the treatment. Each phase was then oxidatively stabilized in order to preserve its structure during carbonization and then carbonized at temperatures ranging from 700 to 1000 °C. The effect of the microstructure, particle morphology and chemical composition of the carbons and also the influence of their carbonization temperature on the electrochemical behaviour as electrode materials in lithium cells were studied.Galvanostatic cycling of lithium test cells using the carbon materials as positive electrodes showed the improvement of the electrochemical performance in both isotropic and anisotropic phases by stabilization with air previous to carbonization. More subtle differences between isotropic and anisotropic samples were evidenced and interpreted in terms of their textural properties. Moreover, the electrochemical impedance spectroscopy (EIS) has been demonstrated to be an interesting technique to elucidate the changes occurred in the electrode interfaces when these coal tar pitch based carbons are cycled.     

AR中间相沥青纺丝性能的研究

以AR中间相沥青为原料,采用元素分析与红外分析手段,研究了沥青原料的结构和组成,通过热台偏光显微镜观察和分析了其流动特性。采用氮压式单孔纺丝机进行熔融纺丝,制备中间相沥青纤维,研究了中间相沥青的可纺性及纺丝工艺对于中间相沥青纤维性能的影响。结果表明,在纺丝温度350℃、纺丝压力0.016MPa与收丝速度220m/min的条件下纺丝得到性能优良的沥青纤维,纺丝连续性好,可连续纺丝约5min。经290℃不熔化处理和1000℃碳化后,得到碳纤维拉伸强度1.45GPa、弹性模量120GPa。     

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.     

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.     

Emission of carcinogenic polyaromatic hydrocarbons in the carbonization of coal pitch

The composition of polyaromatic hydrocarbons liberated at different carbonization rates of coal pitch in an inert atmosphere is studied. The benz[a]pyrene equivalent is calculated. It is shown that reducing the carbonization rate increases the emissions of carcinogenic polyaromatic hydrocarbons.     

Effects of the molecular structure from pitch fractions on the properties of pitch-based electrospun nanofibers

Mesophase pitch was separated into different pitch fractions to investigate the effect of pitch fractions on the properties of their nanofibers prepared by electrospinning. The evolution of different pitch fractions-derived nanofibers during stabilization and carbonization were explored, and the properties of the resultant carbon nanofibers (CNFs) as electrode materials for supercapacitor were compared. Results indicated that the hexane insoluble-toluene soluble (HI-TS) and toluene insoluble-tetrahydrofuran (THF) soluble (TI-THFS) fractions had good spinnability due to their narrow molecular weight distribution. Moreover, compared with HI-TS and THF insoluble (THFI), TI-THFS consisted of appropriate aromaticity and branched alkyl groups which promoted the stabilization and carbonization behaviors of its nanofibers, resulting in maintaining ideal fiber morphology of TI-THFS-derived nanofiber due to the mitigation of their exothermic reactions. Meanwhile, the TI-THFS-derived CNFs presented the highest surface area of 543 m² g⁻¹ and exhibited an excellent specific capacitance of 167 F g⁻¹ at 0.5 A g⁻¹ in 6 M KOH electrolyte.     

Some aspects of the role of coal thermoplasticity and coke structure in coal gasification. 2. The effects of pressure and heating rate on dilatometric parameters and optical anisotropy development

An examination of the influence of pressure and heating rate on the thermoplastic properties of a weakly coking coal and of coal with various pitch-like additives was carried out using a high pressure dilatometer. Pressure up to 4 MPa markedly increased the swelling properties and increased the plastic range by decreasing the softening temperature, but the effects of pressure were strongly influenced by rate of heating with high heating rates enhancing the effects. Additions of tar or pitch also enhanced swelling at low pressure. The solid carbonization residues from the dilatometer were examined by polarized light microscopy to determine the content and composition of optically anisotropic species. The anisotropic content was increased by increases in pressure and heating rate and pitch additives enhanced the anisotropic content, especially at low pressure, without affecting the composition of the anisotropy. No direct correlations exist between the dilatometric parameters and the optical anisotropy but their dependence on the conditions emphasizes that when considering high pressure gasification of coal, it is necessary to obtain data under appropriate conditions.     

Effect of pitch powder addition on the microstructure and properties of carbon blocks for blast furnace

The phase composition and microstructural evolution of pitch-containing matrix sample with additive of silicon had been compared with pitch-free or resin-containing matrix sample to illustrate the strengthening effect of pitch. Two different pitch powders (CARBORES^@P and High temperature pitch) were then incorporated into carbon blocks, respectively and the effect of pitch powder addition on microstructure and properties of carbon blocks fired at 1000?°C and 1400?°C in a coke bed was evaluated systematically. The results showed that compared with amorphous carbonized resin, carbonized pitch was a kind of highly graphitized carbon and could react with silicon and form SiC whiskers at 1400?°C. In carbon blocks, pitch powder accelerated the formation of AlN at 1000?°C and growth of β-SiC whiskers at 1400?°C, respectively, which enhanced the cold compressive strength, thermal conductivity and hot metal erosion resistance of carbon blocks. Moreover, carbon blocks containing CARBORES^@P pitch with higher carbon yield exhibited better properties because of formation of more ceramic whiskers. The strengthening mechanism of pitch powder for carbon blocks was attributed to the pore-blocking effect of pitch carbonization and more in-situ formed whiskers derived from the reaction between carbonized pitch with silicon at 1400?°C.     

中间相沥青熔纺异形纤维的工艺研究 Ⅰ.中间相沥青的性质与异形喷丝板的设计

讨论了用于纺制异形纤维的两种中间相沥青的性质，并根据中间相沥青熔体的模口膨化比等性质，设计制造了用以纺制中空、条形、Ｙ形等异形纤维的喷丝板。异形喷丝孔的当量直径、截面积、孔长等特征尺寸决定了熔体在喷丝孔中的流变行为，建议采用当量异形度作为纤维的异形度指标。     

Formation mechanism of carbon foams derived from mesophase pitch

Carbon foams were prepared from mesophase pitch using foaming, carbonization and graphitization processes. The physical and chemical properties of the mesophase pitch during thermal treatment were studied by Fourier transform infrared spectroscopy, thermogravimetry, mass spectroscopy, rheometry and scanning electron microscopy. The results suggest that gases released from the pitch dissolve, saturate, nucleate and grow in the molten pitch during foaming. Then the resultant bubbles coalesced with the neighboring bubbles driven by the surface tension of the molten pitch. This coalescence generates a shear stress to force aromatic planes of the pitch to arrange regularly and paralleled to the axis of a ligament. The growth of bubbles stopped when the pitch became semi-coke at a temperature above 733 K. The viscosity and surface tension of the molten pitch are major factors that influence the growth of bubbles. After carbonization at 1073 K and graphitization at 2873 K, the well aligned aromatic planes in the foams evolve into highly aligned graphitic structures.     

Carbonization of an anthracene oil extract of Akabira (Japan) coal

The carbonization of a non-hydrogenated extract (STC) from a low-rank coal (C, 83 wt%) of high fluidity was studied as single carbonizations and as co-carbonizations with additives, an objective being the production of needle-coke. The coke from STC had an optical texture of fine-grained mozaics; however, fractionation followed by co-carbonizations were effective in modifying carbonization properties. The lighter fraction of STC could give a coke with flow texture but in reduced yield. The addition of hydrogenated Ashland A240 pitch (HA240) in a quantity as low as 20% could effectively modify the carbonization properties of STC. A novel co-carbonization, in which an additive such as dihydroanthracene is recovered at the latter stage of the carbonization in the dehydrogenated form, was found to be effective also, although a relatively large amount of the additive was required. Among the non-hydrogenated additives, Ashland A240 pitch was the most effective in modifying the STC. The cocarbonization of fractionated STC reduced the quantity of additive required while maintaining a reasonable coke yield. Some practical aspects for the production of needle-coke from STC are discussed.     

The mesophase and high modulus carbon fibers from pitch

The evolution of the basic carbonization studies which led to the development of carbon fibers from mesophase pitch is described. The structure and properties of these fibers and comparisons with carbon fibers from other precursors are also discussed. Several basic areas related to fibers, the mesophase, and the mechanism of carbonization require further investigation.     

Carbon foams with high compressive strength derived from mixtures of mesocarbon microbeads and mesophase pitch

Carbon foam with relatively high compressive strength and suitable thermal conductivity was prepared from mixtures of mesocarbon microbeads (MCMBs) and mesophase pitch, followed by foaming, carbonization and graphitization. The influence of addition amount of MCMB on the properties of as-prepared carbon foams was investigated in detail. Results showed that addition of MCMBs into mesophase pitch could significantly reduce the amount and length of cracks in carbon foams, which results in increase of compressive strength of carbon foams. Carbon foam with high compressive strength of 23.7 MPa and suitable thermal conductivity of 43.7 W/mK, was obtained by adding 50% MCMBs into mesophase pitch, followed by foaming, carbonization and graphitization.     

Carbonization of coal pitch with reduced carcinogenic hydrocarbon emissions

The carbonization of coal pitch in the presence of an additive (5?C14%) that contains sulfone groups is considered. The quantity of pitch sublimates is reduced, along with their content of carcinogenic polycyclic aromatic hydrocarbons. In terms of benz[a]pyrene, the reduction in carcinogenic effect is 300% or more. The benz[a]pyrene content in the waste gas is studied throughout the carbonization process: it is a maximum at 750?C800°C, on account of its high-temperature synthesis in the gas phase.     

高温煤焦油沥青黏结剂碳化固结作用在炭质型材中的应用与研究进展

高温煤焦油沥青（high temperature coal tar pitch,HTCTP）具有优良的润湿性和黏结性,可用作黏结剂。HTCTP黏结剂能与炭质颗粒物料产生良好的固结作用,因此在不同类型炭质型材的制备中获得广泛的应用与研究,HTCTP高温过程的黏结性能及碳化固结作用效果决定了炭质型材的机械强度和理化性能。本文综述了HTCTP作黏结剂制备炭质型材的一般工艺过程和相关研究进展,梳理了不同应用领域对HTCTP碳化固结作用的共性机制和个性特点,总结了HTCTP的性能影响因素及碳化固结作用机理。通过分析HTCTP不同组分在碳化固结过程中的作用及转化过程,揭示HTCTP碳化固结作用与炭质型材机械强度的关联机制及影响碳化固结强度的关键因素,提出强化HTCTP碳化固结作用的措施,提升HTCTP黏结剂在炭质型材制备中的应用效果。