Fundamental studies and pilot verification of an olefins/aromatics-rich chemical production from crude oil dehydrogenation catalytic pyrolysis process

Abstract Crude oil dehydrogenation catalytic pyrolysis (DCP) was carried out by fundamental studies and pilot verification. Ca/ZSM-5 catalysts were used to maximize production of light olefins and aromatics. At temperature of 600 °C, fundamental studies showed that 3%Ca/ZSM-5 (3Ca/ZSM-5) catalyst had the optimum dehydrogenation catalytic pyrolysis activity by pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) and small-sized fluidized bed reactor tests. It was found that there were highest alkenes of 75.30% in volatile products by Py-GC/MS. Furthermore, there were highest C2-C4 olefin yield (34.34 wt%) with a selectivity of 78%, while there were 44.42 wt% aromatics with a selectivity of 86% by fluidized bed reactor tests. Then, scale-up downer pilot tests were verified technical feasibility with 3Ca/ZSM-5 catalyst. C2-C4 olefins reached 36.23 wt% with a selectivity of 70%. Moreover, there were 38.04 wt% aromatics. Apparent activation energy of DCP with 3Ca/ZSM-5 catalyst ranged from 40 to 170 kJ∙mol−1. Last, the mechanism of DCP process was proposed. Excellent chemical yield and selectivity were achieved in DCP process of crude oil, which can provide a guidance for industrial application of crude oil to chemicals.