Superacid ternary ZrO2 SiO2 SnO2 oxide has been synthesized by the sol-gel method with a different atomic ratio Zr:Si:Sn. The highest strength of acid sites has been observed in the ranges of 20 ≤ Zr4+ ≤ 29, 60 ≤ Si4+ ≤ 67, 11 ≤ Sn4+ ≤ 20 at.%. According to the XPS spectra and 119Sn, 29Si MAS NMR spectra of ZrO2 SiO2 SnO2 a partial shift of electron density from zirconium to silicon ions was observed resulting in the formation of superacid Lewis sites. It was shown that superacid Zr29Si60Sn11 mixed oxide efficiently catalyzes acylation of toluene with acetic anhydride at 423 K in a flow reactor with 45% conversion of anhydride at 100% selectivity towards p-methylacetophenone.
Catalytic conversion of fructose to levulinic and formic acids over tin-containing superacid (H0 = −14.52) mixed oxide was studied. Mesoporous ZrO2–SiO2–SnO2 (Zr:Si:Sn = 1:2:0.4) was synthesized by the sol–gel method. The fructose transformation was carried out in a rotated autoclave at 160–190 °C for 1–5 h using a 20 wt.% aqueous solution. The results showed that doping ZrO2–SiO2 samples with Sn4+ ions improved both fructose conversion and selectivity toward levulinic and formic acids. Under optimal conditions of 180 °C, 3.5 h and fructose to catalyst weight ratio 20:1, levulinic and formic acids yields were 80% and 90%, respectively, at complete fructose conversion. At this, humic substances formed in the quantity of 10 wt.% based on the target products.
The study is directed to the search of a simple effective catalyst for ethyl lactate obtained from fructose as renewable raw material. A series of SnO2-containing oxides prepared by impregnation of alumina were characterized by several techniques in order to determine their textural and acid-base properties. The transformation of a 13% fructose solution in 98% ethanol over SnO2/Al2O3 catalysts using autoclave rotated with 60 rpm at 160 °C for 3 h was studied. It was found that doping SnO2/Al2O3 samples with ZnO improves selectivity towards ethyl lactate. The supported SnO2-ZnO/Al2O3 catalyst provides 100% fructose conversion with 55% yield of ethyl lactate at 160 °C. A possible scheme of fructose transformation into ethyl lactate on L-acid IVSn4+ sites is discussed.
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