Phase transition behavior and mesophase aging phenomenon during liquid-state carbonization of FCC decant oil

[Display omitted] •Polymerization-dependent phase transition within isotropic matrix is multi-stage self-assembly.•Mesogen association are tightly related to its configuration and size distribution.•Fractal self-assemblies are formed via reactions-limited cluster–cluster aggregation.•Mesophase aging is proposed and illustrated by gradual intra- and intermolecular aromatization.•Suppressing mesophase aging during isotropic transition is key to obtain spinnable mesophase pitch. The FCC decant oil (FCC-DO), primarily comprising 2- to 5-ring aromatic hydrocarbons with short alkyl side-chains, is widely acknowledged as the optimal precursor for the production of spinnable mesophase pitch, thus achieving its high-value utilization. The preparation of spinnable mesophase pitch from FCC-DO faces the challenge associated with achieving both high mesophase content and low softening point. To address this challenge, the phase separation behavior of the isotropic matrix and the aging phenomenon of coexisting anisotropic phases are examined using high-temperature centrifugation and advanced analytical techniques. The phase transition behavior of isotropic matrix can be described by a multi-stage continuous self-assembly induced by polymerized reactions. And this dynamic assembly process is tightly related to “steric hinderance effect” and “solvent dispersion effect”, which are mainly affected by the configuration and size distribution of formed mesogens respectively. Meanwhile, the formed anisotropic phase gradually undergoes two-staged time-dependent aging behavior, leading to poor compatibility of sub-fractions and then deterioration of melt fluidity. The initial aging of the mesophase is characterized by an almost unchanged molecular weight distribution, but a transformation of molecular configuration from a semi-rigid skeleton to a rigid one. This transformation is caused by intramolecular condensation resulting from the removal of the α-CH3 shielded by adjacent aromatic rings and dehydrogenation of naphthenic rings. When the previously-formed anisotropic phase under the liquid-state carbonized conditions for a long time, the second-stage aging of mesophase is readily triggered through the elimination of the α-CH3 not shielded by adjacent aromatic rings. This gives rise to the intermolecular polymerization and a shift towards higher molecular weight. This study provides insights into the preparation of excellent melt-fluidity mesophase pitch by promoting the rapid