Petroleum-based impregnating pitches were prepared from pyrolysis fuel oil (PFO) using a two-step heat treatment without a separation process. The pressurized heat treatment, the first step, was used to improve the properties of the pitches and enhance the product yield by promoting the cracking and polymerization of the components in the PFO. An atmospheric heat treatment as the second step was used only to synthesize the impregnating pitches from the liquid pitches prepared during the first step. The prepared impregnating pitches had the properties of a commercial petroleum-based impregnating pitch. The impregnation performance was evaluated by HT-XRD and an impregnation test. The HT-XRD results showed changes in the stacked structure of the pitches at the impregnation temperature. The bulk density of the carbon block was increased to 14.3% and the porosity was reduced by 10.3% after the impregnation/recarbonization process. The high reaction temperature during the first step induced the formation of quinoline insoluble (QI) components during the second step of the treatment, and the QI components adversely affected the impregnation process.
We demonstrated an effective way of preparing melt spinnable mesophase pitches via catalytic hydrogenation of petroleum residue (fluidized catalytic cracking-decant oil) and their subsequent thermal soaking. The mesophase pitches thus obtained were analyzed in terms of their viscosity, elemental composition, solubility, molecular weight, softening point and optical texture. We found that zeolite-induced catalytic hydrogenation under high hydrogen pressure contributed to a large variation in the properties of the pitches. As the hydrogen pressure increased, the C/H ratio decreased, and the solubility in n-hexane increased. The mesophase pitch with entirely anisotropic domains of flow texture exhibited good meltspinnability. The mesophase carbon fibers obtained from the catalytically hydrogenated petroleum residue showed moderate mechanical properties.
Coal-tar pitch, a feedstock which can be heat-treated to create graphite, is composed of very complex molecules. Coal-tar pitch is a precursor of many useful carbon materials (e.g., graphite, carbon fibers, electrodes and matrices of carbon/carbon composites). Modified coal-tar pitch (MCTP) was prepared using two different heat-treatment methods and their properties were characterized and compared. One was prepared using heat treatment in nitrogen gas; the other was prepared under a pressure of 350 mmHg in air. The MCTPs were investigated to determine several properties, including softening point, C/H ratio, coke yield, formation of anisotropic mesophase and viscosity. The MCTPs were subject to considerable changes in chemical composition due to condensation and polymerization in the used-as-received coal-tar pitch after heat-treatment under different conditions. The MCTPs showed considerable increases in softening point, C/H ratio, and coke yield, compared to those of as-received coal-tar pitch. The MCTP formed by heat-treatment in nitrogen showed isotropic phases below 350˚C for 1 h of soaking time. However, MCTP heat-treated under high pressure (350 mmHg) showed isotropic phases below 300˚C, and showed anisotropic phases above 350˚C, for 1 h of soaking time. The viscosity of the MCTPs increased with increase in their softening points.
Two pitches with different average molecular structures were electrospun and compared in terms of the properties of their fibers after oxidative stabilization, carbonization, and activation. The precursor with a higher molecular weight and greater content of aliphatic groups (Pitch A) resulted in better solubility and spinnability compared to that with a lower molecular weight and lower aliphatic group content (Pitch B). The electrical conductivity of the carbon fiber web from Pitch A of 67 S/cm was higher than that from Pitch B of 52 S/cm. The carbon fiber web based on Pitch A was activated more readily with lower activation energy, resulting in a higher specific surface area compared to the carbon fiber based on Pitch B (Pitch A, 2053 m2/g; Pitch B, 1374 m2/g).
The modification of coal-tar pitch has been carried out by heat treatment of pitch at different temperatures in the range (300˚-400℃) for different times (2-5 hrs) in air and nitrogen. The pitch heat treated in air at lower temperature (300℃) exhibit increase in softening point by 20℃ as compared to only 2℃ when treated in nitrogen. The changes are faster in air than in pure nitrogen. Pitch as such as well as after heat treatment were further treated with metal complexes by solution route. Silver intake has been found to increase from 0.5 to 0.8 % in nitrogen treated pitch while the uptake is found to decrease for pitches treated in air at 350℃ for 5 hrs. Experiments have also been made to incorporate silver into PAN and PAN-ox fibers through solution route. The metal intake has been found to be more in PAN-ox fibers than in PAN as such. Metal loaded carbon composites have been made by using metal loaded fibers as well as cokes. These composites as such exhibit higher surface oxygen complexes but decrease after activation.
Coal tar pitch was chemically modified with 10 wt% benzoquinone (BQ) to raise the softening point of isotropic pitch precursor and the precursor was melt-spun into pitch fibers, stabilized, carbonized and activated with steam at 900℃. The weight loss of carbon fiber-benzoquinone (CF-BQ) increased with the increase of activation time like other fibers, but was lower than those of Kureha fiber at the same activation time in spite of larger geometric surface area. Those adsorption isotherms fitted into 'Type I' according to Brunauer, Deming, Deming and Teller classification. However, there was very thin low-pressure hysteresis that lower closure points of the hysteresis are about 0.42-0.45. From the pore size distribution curves, there might be some micropores having narrow-necked bottle; a series of interconnected pore is more likely than discrete bottles. FT-IR studies showed that the functional groups such as carboxyl, quinone, and phenol were introduced to ACFs-BQ surface after steam activation. Methylene blue decolorization and iodine adsorption capacity of ACF-BQ increased linearly with the increase of specific surface area and was larger than that of ACF-Kureha at the same specific surface area.