Catalytic conversion of asphaltenes to BTXN using metal-loaded modified HZSM-5
Linyang Wang, Qiang Wang, Yongqi Liu, Qiuxiang Yao, Ming Sun, Xiaoxun Ma
中国化学工程学报. 2022, 49(9):
HZSM-5 zeolites with Si/Al ratios of 20, 35, 50 and 65 were prepared by the directing crystallization process of silicalite-1 seeds. The influence of Si/Al ratios on the production of benzene, toluene, xylene and naphthalene (BTXN) originated from asphaltenes catalytic pyrolysis was explored by adopting Py-GC/MS. Modified Z5-50 zeolites were prepared by various metal ions (Ni2+, Mo6+, Fe3+, and Co2+) with different loading rates (3% (mass), 5% (mass), 7% (mass), and 9% (mass)) and the physical and chemical properties of these zeolites were characterized by XRD, SEM, ICP-OES, XPS, NH3-TPD, FTIR, Py-IR and N2 adsorption-desorption isotherm. In addition, they were employed to catalyze the conversion of asphaltenes pyrolysis production to BTXN using Py-GC/MS. Results show that the highest relative content of aromatics has been obtained over HZSM-5 with Si/Al ratio of 50 (Z5-50), reaching 61.87%. Besides, the loading of Ni, Mo, Fe, and Co on Z5-50 leads to an increase of acid strength and provides new active sites. The relative content of BTXN increases by 3.17% over 3Ni-Z5, which may be ascribed to that Ni promoted the conversion of polycyclic aromatic hydrocarbons (PAHs) to monocyclic aromatics due to the cracking of aliphatic side chains of PAHs and the decrease of phenolic activation energy. While under the catalysis of 5Mo-Z5, the relative content of aromatics and BTXN augmented by 5.75% and 4.02%, respectively. In addition, the highest relative content of aromatics reaches 70.09% when the loading rate of Fe was 7% (mass), and the relative content of BTXN increases from 25.87% to 29.42%. The results demonstrate that the active sites provided by different metal species expressed diverse effects on BTXN. Although the Brønsted/Lewis acid ratios of HZSM-5 modified by metal decreased, the acid strength and the relative content of BTXN both increased, which illustrated that there is a synergistic catalysis with the Brønsted acid sites and Lewis acid sites provided by metal species. In general, the performance of the catalyst is affected by the pore structure, acidity and metal active sites. Moreover, the possible formation mechanism of BTXN derived from asphaltenes catalytic pyrolysis was proposed on the basis of structural features and catalytic performances of a series of zeolites.