Carbonization properties of carbonaceous substances oxidized by air blowing—I: Carbonization behaviors and chemical structure of residual oils oxidized by air blowing

The carbonization process of oxidized oils was investigated by the successive observation of the cokes at several intermediate stages with particular attention to the cocarbonization compatibility of the components, in order to understand how the medium mosaic texture was developed from the oxidized oils. When the oxidized oil was carbonized, very small anisotropic spheres appeared in the matrix, but, being fixed into the mosaic texture, they formed clusters with limited growth of their diameters. The n-hexane insoluble (nHI) and the n-hexane soluble (nHS) components in the, oxidized oil produced isotropic and flow textures in the cokes, respectively. These components did not allow the smooth growth of the anisotropic spheres because of their poor compatibility. Cocarbonization with some proper additives was found effective both in developing a flow texture from the nHI of the oxidized oil and producing a high coke yield. Chemical analyses of the components were performed in order to explain the compatibility.     

Modifying ability of Ql-free coal-tar pitch to develop optical anisotropy in co-carbonizations

Carbonization properties of a Ql-free coal-tar pitch (CTP-ASM) prepared by selective precipitation were studied to evaluate it as a source for needle-coke. Its modifying ability for production of needlecoke in co-carbonizations with principal carbonizing substances which gave cokes of mozaic texture in single carbonizations was estimated by changing mixing ratios. The shape and size of the anisotropic optical texture in the co-carbonized coke were measured by point counting. CTP-ASM and Ashland A240, of eight additives, had the highest modifying ability in the co-carbonizations with Khafji vacuum residue. Both contained ca. 6% benzene-insolubles (Bl), and had f_a values of ≈0.9. Other additives of either lower or higher Bl or f_a showed less modifying ability. The modifying susceptibility of principal carbonizing substances varies with their structure and properties. Based on a systematic investigation of co-carbonizations the compatibility between a principal carbonizing substance and an additive is discussed from a viewpoint of their structural parameters.     

Reactivities of Blair Athol and Nang Tong coals in relation to their behavior in PFBC boiler

The combustion reactivities of Blair Athol (BA) and Nang Tong (NT) coals were measured by thermogravimetry to understand their different behaviors in the PFBC boiler. The reactivity of BA was much the same as that of NT coal but their chars showed different characteristics. BA char of higher surface area (25 m²/g) showed slightly higher reactivity than that of NT char of smaller surface area (7 m²/g). BA coal showed heterogeneous ignition even at its particle size of as large as +355 μm while NT coal showed homogeneous ignition at the average particle size over 75 μm heterogenous one occurring with finer particle size (−75 μm). Higher calorific value of BA volatile matter and higher reactivity of its char than those of NT coal causes of its heterogeneous ignition with an intense DTA peak, which may lead to local heating at its combustion and to yield reactive CaO from limestones causing of bed materials agglomeration in the PFBC.     

Isotropic carbon and graphite fibers from chemically modified coal-tar pitch

A precursor for a general purpose carbon fiber was prepared from coal tar pitch (CP) modified with 10 % p-benzoquinone (BQ) at 380 ?C for 3 hours. Such a modification raised the softening of the pitch from 85 ?C to 271 ?C at a yield of 43 %. The modified pitch was spun smoothly at a rate of 480 m/min into a fiber of 20 Μm diameter. The fiber was stepwise stabilized at 236 ?C (5 ?C/min) and 312 ?C (1 ?C/min) for 3 hours at each temperature. Successively,carbonization and graphitization were performed at 1,000 ?C and 2,400 ?C, respectively, for one hour. Both the carbonized and graphitized fibers exhibited tensile strength of 570 MPa. The structural parameters of carbon and graphite fibers were their orientation values of 56.2 and 58.1 %, relatively low Lc(002) of 11.24 and 25 å, and large interlayer spacing (d₀₀₂) of 3.86 and 3.49 å, respectively.     

Blending mesophase pitch to improve its properties as a precursor for carbon fibre Part 1 Blending of PVC pitch into coal tar and petroleum-derived mesophase pitches

The blending of mesophase pitch with isotropic PVC pitch was studied to improve their properties as a precursor for carbon fibre. PVC pitch prepared at 420° C which remained almost isotropic was found to be miscible with coal tar-derived mesophase pitch without reducing the anisotropic content and spinnability. The tensile strength of pitch fibres remained unchanged by the blending; however, the reactivity for stabilization was enhanced. The resultant carbon fibres from the blend exhibited slightly higher tensile strength. In contrast, petroleum-derived mesophase pitch failed to dissolve the PVC pitch, leaving a number of isotropic droplets. The structural factors of mesophase pitches with regard to their compatibility with PVC pitches are briefly discussed.     

Modification of mesophase pitch by blending Part 2 Modification of mesophase pitch fibre precursor with thermoresisting polyphenyleneoxide (PPO)

Polyphenyleneoxide was blended in amounts of 5 or 10 wt% into petroleum-derived mesophase pitch to reinforce the pitch fibre before the oxidative stabilization to achieve better handling properties. Although polyphenyleneoxide was fusible but hardly soluble in the mesophase pitch even at a spinning temperature of 350° C, blended pitch could be smoothly spun into pitch fibre 10m diameter, as could the parent pitch. Fibrous polyphenyleneoxide of less than 1m diameter was homogeneously dispersed in the pitch fibre, being arranged along the fibre axis. Such fibrous polyp henyleneoxide reinforced the pitch fibre considerably. The fibrous substances at the centre of the fibre disappeared in the carbonized fibre at 1300° C after oxidation at 250° C, although some short ones were observed in the skin region of the fibre, suggesting that polyphenyleneoxide was co-carbonized to be assimilated with mesophase pitch at the centre of the fibre, where the effects of oxidation may be rather limited. The oxidation reactivity and its mechanical strength after carbonization were slightly lower in comparison with those of the parent mesophase pitch.     

Preparation of an activated carbon artifact: oxidative modification of coconut shell-based carbon to improve the strength

Coconut shell-based activated carbon was oxidized in aq. H₂SO₄, HNO₃ and H₂O₂ to induce surface oxygen functional groups on its surface and to increase the mechanical strength of the resultant activated carbon artifact with PVB as a binder. Although all oxidation was confirmed to significantly increase the strength, aq. H₂O₂ was found to be most effective, giving strength as high as 6000 kPa, which is believed to be sufficient for the electrode of an electric double layer capacitor (EDLC). The increase of CO₂ evolving groups induced on the surface of activated carbon appears to be responsible for the strength increase. There was an optimum extent of oxidation for the strength as well as the performance of the electrode. Too much oxidation reduces the electrical conductivity of the activated carbon. Facile oxidation by aq. H₂O₂ can be recommended as a practical modification of the surface since it takes place safely below 100°C without releasing any harmful gas.     

Carbonization of coals into anisotropic cokes: 7. Copreheat-treatment under short contact-time conditions at high temperature

The copreheat-treatment of non-fusible and slightly fusible coals with A240 and hydrogenated A240 under high temperature-short contact-time conditions around 500 °C has been examined in an attempt to produce a formed coke with better anisotropic development. These conditions shortened the copreheat-treatment time and provided better anisotropic development in the resultant coke after carbonization. Effectiveness of short contact-time has been discussed in terms of the extent of depolymerization of coal molecules suitable for anisotropic development, this being related to coal liquefaction under similar conditions.