Kinetic and Thermodynamic Study of Vacuum Residue Cracking over Cerium-Modified Metakaolinite Catalyst

Abstract

Catalytic upgrading of vacuum residue (VR) is critical for enhancing fuel yield and reducing waste in petroleum refining. This study explores VR cracking over a novel cerium-loaded acidified metakaolinite catalyst (MKA800–20%Ce) prepared via calcination at 800 ◦C, acid leaching, and wet impregnation with 20 wt.% Ce. The catalyst was characterized using FTIR, BET, XRD, TGA, and GC–MS to assess structural, textural, and thermal properties. Catalytic cracking was carried out in a fixed-bed batch reactor at 350 ◦C, 400 ◦C, and 450 ◦C. The MKA800@Ce20% catalyst showed excellent thermal stability and surface activity, especially at higher temperatures. At 450 ◦C, the catalyst yielded approximately 11.72 g of total liquid product per 20 g of VR (representing a ~61% yield), with ~3.81 g of coke (~19.1%) and the rest as gaseous products (~19.2%). GC-MS analysis revealed enhanced production of light naphtha (LN), heavy naphtha (HN), and kerosene in the 400–450 ◦C range, with a clear temperature-dependent shift in product distribution. Structural analysis confirmed that cerium incorporation enhanced surface acidity, redox activity, and thermal stability, promoting deeper cracking and better product selectivity. Kinetics were investigated using an eight-lump first-order model comprising 28 reactions, with kinetic parameters optimized through a genetic algorithm implemented in MATLAB. The model demonstrated strong predictive accuracy taking into account the mean relative error (MRE = 9.64%) and the mean absolute error (MAE = 0.015) [MAE: It is the absolute difference between experimental and predicted values; MAE is dimensionless (reported simply as a number, not %). MRE is relative to the experimental value; it is usually expressed as a percentage (%)] across multiple operating conditions. The above findings highlight the potential of Ce-modified kaolinite-based catalysts for efficient atmospheric pressure VR upgrading and provide validated kinetic parameters for process optimization.