Rational synthesis of silylated Beta zeolites and selective ring opening of 1-methylnaphthalene over the NiW-supported catalysts

[Display omitted] •The distribution of acid sites in zeolites was modified by silylation with various alkyl chains.•Large silylation agents induce to deposit SiO2 on the external surface of zeolites.•NiW/silylated zeolite alters the balance of metallic and acidic functions.•Selective ring opening of 1-methylnaphthalene by NiW/silylated zeolite was tested.•The optimal balance of bi-functional catalysts improve conversion and selectivity. Heavy oil has been by-produced from refinery and petrochemical processes, and its use as low-value fuels has been restricted by stricter environmental regulations due to heavy molecules, multi-ring aromatics, and high sulfur content. In a bi-functional catalyst system of metal and zeolitic acid, balancing metallic (from metal element) and acidic function (from zeolite elements) is essential for harnessing the selective ring opening (SRO) reaction with the aim of upgrading the heavy oil. Here, we report a synthetic strategy to control the acid site distribution of Beta zeolite through the silylation reaction with tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), and tetrabutyl orthosilicate (TBOS) as silylation agents. As the size of alkyl chain group in the silylation agents gets larger, the silylation agents were suppressed to spread into the channels and thus the formation of SiO2 layer was intentionally occurred on the external surface of the zeolite. Resulting from the selectively deposited SiO2 layer, NiW metals supported on each silylated Beta zeolite altered the metal distribution and further the balance of metallic and acidic function. NiW catalyst supported on TBOS-silylated Beta zeolite exhibited the best catalytic performance toward the SRO reaction of 1-methylnaphthalene in a fix-bed reaction system, proving the optimal balance of metallic and acidic functions. We expect that this study will benefit the control over the selective silylation reaction in order to optimize the balance of metallic and acidic functions in the bi-functional catalysts, and, hence, to promote properly aromatic saturation (hydrogenation) and ring opening (hydrocracking) for selective ring opening products.