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.

The production of industrially demanded polymer precursor ethylene glycol (EG) from biomass‐accessible aqueous glycolic acid (GA) was investigated in this study. The systematic investigation of different active metals as well as, for the first time, various support materials revealed Ru/TiO2 and Ru/ZrO2 to be the most active catalysts in the heterogeneously catalyzed reduction of GA with molecular H2. Catalytic activity is enhanced by facilitated reduction of the active Ru species due to metal‐support interactions. An assessment of several other catalyst properties (metal surface area, acid properties, porosity) revealed that high metal dispersion is also beneficial. Up to 94 % GA conversion and 95 % selectivity for EG were obtained under optimized and mild reaction conditions (105 °C, 60 bar H2 pressure, 23 h, Ru/TiO2 as catalyst). This shows that the heterogeneously catalyzed reduction of biomass‐derived aqueous GA solutions can be a promising alternative for the renewable production of EG.

No abstract

No abstract

Ethylene glycol (EG) is obtained by a novel, two‐step approach combining a biotechnological and a heterogeneously catalyzed step. First, microalgae are cultivated to photobiocatalytically yield glycolic acid (GA) by means of photosynthesis from CO2 and water. GA is continuously excreted into the surrounding medium. In the second step, the GA‐containing algal medium is used as feedstock for catalytic reduction with H2 to EG over a Ru/C catalyst. The present study focuses on the conversion of an authentic algae‐derived GA solution. After identification of the key characteristics of the algal medium (compared to pure aqueous GA), the influence of pH, numerous salt additives, pH buffers and other relevant organic molecules on the catalytic GA reduction was investigated. Nitrogen‐ and sulfur‐containing organic molecules can strongly inhibit the reaction. Moreover, pH adjustment by acidification is required, for which H2SO4 is found most suitable. In combination with a modification of the biotechnological process to mitigate the use of inhibitory compounds, and after acidifying the algal medium, over Ru/C a EG yield of up to 21 % even at non‐optimized reaction conditions was achieved.