Effect of hierarchical porosity in Beta zeolites on the Beckmann rearrangement of oximes

0506755 - ÚFCH JH 2020 RIV GB eng J - Článek v odborném periodiku
Linares, M. - Vargas, C. - Garcia, A. - Ochoa-Hernández, Cristina - Čejka, Jiří - Garcia-Munoz, R. A. - Serrano, D. P.
Effect of hierarchical porosity in Beta zeolites on the Beckmann rearrangement of oximes.
Catalysis Science &Technology. Roč. 7, č. 1 (2017), s. 181-190. ISSN 2044-4753. E-ISSN 2044-4761
Grant CEP: GA ČR GBP106/12/G015
Institucionální podpora: RVO:61388955
Klíčová slova: cyclohexanone-oxime * catalytic-properties * epsilon-caprolactam * active-sites * organofunctionalized seeds * cyclododecanone oximes
Obor OECD: Physical chemistry
Impakt faktor: 5.365, rok: 2017
Způsob publikování: Omezený přístup

Hierarchical Beta zeolites with different Si/Al molar ratios, synthesized by crystallization of silanized protozeolitic units, were investigated in the liquid-phase Beckmann rearrangement of cyclohexanone and cyclododecanone oximes. The hierarchical Beta samples contain mesopores with sizes in the range 2.0-6.0 nm, as well as the typical zeolite micropores, showing a great contribution of the mesopore/external surface area (300-328 m(2) g(-1)) to the BET surface area (706-763 m(2) g(-1)) and increased Lewis acidity compared to conventional Beta zeolites. Diffusional and steric limitations were found to strongly influence the oxime Beckmann rearrangement as enhanced conversions were obtained with the hierarchical Beta zeolites. The largest differences between conventional and hierarchical Beta zeolites were denoted with the bulkier oxime, i.e. in the rearrangement of cyclododecanone oxime. In this case, two stages are clearly observed in the evolution of the oxime conversion along the reaction time, with a plateau being reached at long reaction times due to deactivation by product inhibition. Hierarchical Beta zeolites exhibited superior performance in both stages compared to reference samples. These results indicate that the use of hierarchical Beta zeolites for oxime Beckmann rearrangement leads to significant improvements in the catalytic behavior compared to conventional Beta samples due to a number of factors: faster intracrystalline diffusion, availability of non-sterically hindered mesopore/surface area and lower deactivation through product inhibition.
Trvalý link: http://hdl.handle.net/11104/0297933