Estimation of catalytic cracking of vacuum gas oil by ZSM-5-and (3-zeolite-containing two-layered and novel three-layered hierarchical catalysts using Curie point pyrolyzer

ZSM-5- and (3-zeolite-containing two-layered hierarchical catalysts (2 L-Z and 2 L-(3) were prepared using a template of malic acid and novel three-layered hierarchical catalysts were also prepared combining mesoporous silica derived from the gel skeletal reinforcement (GSR) method with hexamethyldisiloxane (HMDS) - acetic anhydride (AA) as reinforcing agents. 2 L-Z and 2 L-(3 catalysts contained mesoporous silica of 50 wt% and microporous zeolite of 50 wt% and were called 2 L-Z-(Z50) and 2 l-(3-(Z50) in which the amount of zeolite is shown in parenthesis. 3 L-co-gel and 3 L-mix, two types of three-layered hierarchical catalysts, were prepared by making GSR-silica in the presence of a 2 L catalyst for the former and by combining GSR-silica-gel with 2 L catalyst for the latter. 3 L catalysts contained 50 wt% of the 2 L catalyst and 50 wt% large-mesoporous GSR-silica and revealed three layered properties of microporous zeolite, small mesoporous silica and large mesoporous silica. Signals of zeolite crystals and amorphous phase were observed in XRD measurement for 3 L catalysts. Both smaller size of mesopores and larger size of mesopores were observed in N2 adsorption-desorption measurement. Vacuum gas oil (VGO) was catalytically cracked using 2 L and 3 L hierarchical catalysts with the use of Curie point pyrolyzer (CPP) method. ZSM-5-containing 3 L catalysts exhibited the lower conversions than corresponding 2 L catalyst, kaolin-mixed catalyst and ZSM-5 single while 3 L-co-gel-(3-(Z25), which included 25 wt% of (3-zeolite, exhibited the highest activity among (3-zeolite-containing catalysts. The higher selectivity for pxylene in xylene mixture was detected in catalytic cracking using 3 L-co-gel-Z-(Z25) and 3 L-mix-Z-(Z25) catalysts. When the relative activity against XRD integral intensity and amounts of acid sites was plotted against average pore diameter derived from N2 adsorption-desorption measurement, the strong correlation was observed, suggesting that the intrinsic activity of active sites of zeolite could be related to the pore size of the whole catalyst.