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Nasl. z nasl. zaslona. Soavtorji: Matjaž Finšgar, Janez Zavašnik, Nataša Novak Tušar, Albin Pintar. Opis vira z dne 17. 2. 2023. Bibliografija: str. 10-12. Abstract.

A systematic structural study of Ni in the Ni/ZSM-5 materials is presented, which is beneficial for any further investigation of the catalytic activities of Ni/ZSM-5 and other metal-modified bifunctional catalysts.

Mesopores in the range of 4 to 5 nm were introduced into zeolite Y (nSi/nAl = 16) by surfactant-templating. This method using a mixture of octadecyltrimethylammonium hydroxide and bromide (C18TAOH/C18TABr) yields a mesoporous zeolite (Y–C18TAOH) with a higher specific mesopore volume and only a small loss in crystallinity and specific micropore volume. After loading with Pt, the two bifunctional catalysts (2.7Pt/Y and 2.6Pt/Y–C18TAOH) were applied in the aqueous-phase hydrogenation of levulinic acid (LA) to γ–valerolactone (GVL) (pH2 = 2.5 MPa, 393 K). Intraparticle mass–transfer limitations present for the catalyst 2.7Pt/Y were not observed in the LA hydrogenation over the catalyst with the hierarchical pore system 2.6Pt/Y–C18TAOH. Changes in the acid and de-/hydrogenation functionality are shown not to be responsible for the high catalytic activity of 2.6Pt/Y–C18TAOH. The presence of additional mesopores in a bifunctional catalyst based on zeolite Y is proven to enhance the mass-transfer properties and the resulting catalytic activity in the aqueous-phase hydrogenation of LA for the first time. Hue-Tong Vu is grateful to Vietnam International Education Development of the Ministry of Education and Training, Vietnam, for funding her doctoral study at Universität Leipzig, Germany. Noemi Linares and Javier García-Martínez acknowledge funding from the European Commission through the H2020-MSCA-RISE-2019 program (Ref. ZEOBIOCHEM – 872102) and the Spanish MINECO and AEI/FEDER, UE through the project RTI2018-099504-B-C21. Noemi Linares thanks the University of Alicante for funding (UATALENTO17-05).

A systematic silylation approach using mono-, di-, and trichlorosilanes with different alkyl chain lengths was employed to enhance the hydrothermal stability of zeolite Y. DRIFT spectra of the silylated zeolites indicate that the attachment of the silanes takes place at surface silanol groups. Regarding hydrothermal stability under aqueous-phase processing (APP) conditions, i.e., pH ≈ 2, 473 K and autogenous pressure, the selective silylation of the zeolite surface using monochlorosilanes has no considerable influence. By using trichlorosilanes, the hydrothermal stability of zeolite Y can be improved significantly as proven by a stability test in an aqueous solution of 0.2 M levulinic acid (LA) and 0.6 M formic acid (FA) at 473 K. However, the silylation with trichlorosilanes results in a significant loss of total specific pore volume and total specific surface area, e.g., 0.35 cm3 g−1 and 507 m2 g−1 for the silylated zeolite Y functionalized with n-octadecyltrichlorosilane compared to 0.51 cm3 g−1 and 788 m2 g−1 for the parent zeolite Y. The hydrogenation of LA to γ-valerolactone (GVL) was conducted over 3 wt.-% Pt on zeolite Y (3PtY) silylated with either n-octadecyltrichlorosilane or methyltrichlorosilane using different reducing agents, e.g., FA or H2. While in the stability test an enhanced hydrothermal stability was found for zeolite Y silylated with n-octadecyltrichlorosilane, its stability in the hydrogenation of LA was far less pronounced. Only by applying an excess amount of methyltrichlorosilane, i.e., 10 mmol per 1 g of zeolite Y, presumably resulting in a high degree of polymerization among the silanes, a recognizable improvement of the stability of the 3 PtY catalyst could be achieved. Nonetheless, the pore blockage found for zeolite Y silylated with an excess amount of methyltrichlorosilane was reflected in a drastically lower GVL yield at 493 K using FA as reducing agent, i.e., 12 vs. 34% for 3PtY after 24 h.