The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in vapor-phase is economically more viable route if compared to reaction in liquid-phase. To improve the GVL yield in the vapor-phase reaction, the optimization of nickel modified zeolite as bi-functional catalyst (Ni/HZSM-5) was studied. Ni/HZSM-5 materials with fixed Al/Si molar ratio of 0.04 and different nominal Ni/Si molar ratios (from 0.01 to 0.05) were synthesized without the use of organic template and with the most affordable sources of silica and alumina. Materials were characterized by X-ray powder diffraction, SEM-EDX, TEM-EDX, pyridine TPD and DRIFTS, H2-TPR, N2 physisorption and isoelectric point. In the synthesized materials, 61–83% of nickel is present as bulk NiO and increases with nickel content. Additionally, in all catalysts, a small fraction of Ni2+ which strongly interacts with the zeolite support was detected (10–18%), as well as Ni2+ acting as charge compensating cations for Brønsted acid sites (7–21%). Increasing the nickel content in the catalysts leads to a progressive decrease of Brønsted acid sites (BAS) and concomitant increase of Lewis acid sites (LAS). When BAS/LAS is approaching to 1 and at the same time the amount of NiO reducible active sites is around 80%, the bi-functional Ni/HZSM-5-3 catalyst (Ni/Al = 0.59) leads to 99% conversion of LA and 100% selectivity to GVL at 320°C. This catalyst also shows stable levulinic acid hydrogenation to GVL in 3 reaction cycles conducted at 320°C. The concerted action of the following active sites in the catalyst is a key element for its optimized performance: (1) Ni metallic active sites with hydrogenation effect, (2) Lewis acid sites with dehydration effect, and (3) nickel aluminate sites with synergetic and stabilizing effects of all active sites in the catalyst.
Fly ash (FA) from lignite coal combusted in different Thermal Power Plants (TPPs) was used for the synthesis of zeolites (FAZs) of the Na-X type by alkaline activation via three laboratory procedures. FAZs were characterized with respect to their morphology, phase composition and surface properties, which predetermine their suitability for applications as catalysts and adsorbents. FAZs were subsequently modified with metal oxides (CuO) to improve their catalytic properties. The catalytic activity of non-modified and CuO-modified FAZs in the total oxidation of volatile organic compounds was investigated. FAZs were studied for their potential to retain CO2, as their favorable surface characteristics and the presence of iron oxides make them suitable for carbon capture technologies. Thin films of FAZs were deposited by in situ crystallization, and investigated for their morphology and optical sensitivity when exposed to pollutants in the gas phase, e.g., acetone. This study contributes to the development of novel technological solutions for the smart and valuable utilization of FA in the context of the circular economy and green energy production.
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INSTITUTE OF ORGANIC CHEMISTRY WITH CENTRE OF PHYTOCHEMISTRY - BAS
INSTITUTE OF ORGANIC CHEMISTRY WITH CENTRE OF PHYTOCHEMISTRY - BAS