Medium- and low-temperature coal tar pitch can be prepared as coal-based mesophase pitch for its high value-added utilization. However, its lower aromaticity and higher content of heteroatoms (especially O atoms) led to a higher content of the resulting mesophase pitch mosaic structure. In this study, mesophase pitch was prepared by co-carbonization of high aromaticity, low oxygen content high-temperature refined pitch (RHCTP) with medium- and low-temperature coal tar refined pitch (RCTP). The impact of various blending ratios on the optical and microcrystalline structures of mesophase pitch was analyzed using polarized light microscopy, X-ray diffraction, and Raman spectroscopy. The addition of RHCTP to modify RCTP significantly enhanced the optical and microcrystalline structures of the co-carbonized products. The optimal blending ratio (R-25%) was obtained. Needle coke prepared from mesophase pitch obtained from R-25% had superior fine fiber structure, lowest average resistivity (157.37 μΩ·m) and high true density (2.125 g/cm3). The thermal conversion behavior of the blended refined pitch during co-carbonation was analyzed using thermogravimetric data of the R-25% sample through four isoconversion methods. The thermal conversion of the R-25% sample occurs in three stages: the first stage follows the Parabola law model, while the second and third stages adhere to the random nucleation and nuclei growth model. This analysis of thermal conversion kinetics offers theoretical insights for optimizing mesophase pitch preparation process conditions and reactor design.
Coal pitch mainly consists of aromatic hydrocarbons, phenolic substances, and aliphatic hydrocarbons, the macromolecular structures formed by these cyclic and chain hydrocarbons through chemical bonding possess diversity and complexity. In this study, medium- and low-temperature coal tar pitch (LCTP) served as the primary material for the production of mesophase pitch via co-carbonization with hydrogenated tail oil (HTO). Aimed to clarify the effects of different amounts of HTO addition and analyze the mechanism of introducing naphthenic and aromatic hydrocarbons on the liquid phase carbonization process. When HTO additive amount is 30%, the carbonized product with the largest content of mature graphite crystals at 25.01%, and the smallest degree of defects. The analytical mechanism demonstrates that the condensation of naphthenic hydrocarbons introduced by HTO produces hydrogen radicals, the hydrogen transfer reaction saturates a significant quantity of free radicals generated within the system, thereby impeding further rapid condensation and curing, and decreasing the viscosity of the system. On the other hand, the aromatic hydrocarbons introduced undergo dehydrogenation and condensation to produce additional polycyclic aromatic hydrocarbons, thereby contributing to a more abundant carbon structure conducive to the development of mesophase pitch. The combined effect of aromatic hydrocarbons and naphthenic hydrocarbons facilitates the slow development of the mesophase structure into a broad-area optical structure. This study provides an effective method for improving the performance of coal-based mesophase pitch, which reduces the production cost and promotes the clean and high value-added utilization of limited resources.
The structure and composition of coal tar pitch are critical in the production of superior needle coke. We used high-temperature refined coal tar pitch (HRCTP) to modify medium–low-temperature refined coal tar pitch (MLRCTP) for needle coke preparation. Various characterization techniques were applied to evaluate the effects of the HRCTP addition on the MLRCTP's structure and composition, and to investigate the microstructural and crystallographic differences in needle coke from different feedstocks. We identified the optimal HRCTP addition level and assessed how carbonization reaction conditions influenced needle coke quality. The findings indicated that HRCTP addition increased the aromatic hydrocarbons content while reducing the heterocyclic compounds and excess alkanes, leading to enhanced structure and composition, which supported the structured development of carbon-based structures during the thermal polycondensation process. Notably, higher HRCTP amounts did not equate to better outcomes. With a 25% HRCTP additive level, the needle coke’s microstructure showed a highly ordered fibrous texture with optimal orientation, the greatest degree of graphitization, and a mature graphite crystal content of 24.84%. Further optimization of the carbonization process demonstrated that very high temperatures might cause the formation of numerous mosaic structures due to disordered radical cross-linking. Properly reducing pressure at high temperatures could promote adequate directional airflow and apply shear force during orderly stacking of the mesophase, thus enhancing the carbon lamellae’s streamline and orientation. Following the carbonization process optimization, the mature graphite crystal content in the needle coke increased from 24.84% to 39.87%.