Correction: Popova et al. Ni-Cu and Ni-Co-Modified Fly Ash Zeolite Catalysts for Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone. Molecules 2024, 29, 99.

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Ni-Cu and Ni-Co-Modified Fly Ash Zeolite Catalysts for Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone.

Monometallic (Ni, Co, Cu) and bimetallic (Ni-Co, Ni-Cu) 10-20 wt.% metal containing catalysts supported on fly ash zeolite were prepared by post-synthesis impregnation method. The catalysts were characterized by X-ray powder diffraction, N2 physisorption, XPS and H2-TPR methods. Finely dispersed metal oxides and mixed oxides were detected after the decomposition of the impregnating salt on the relevant zeolite support. Via reduction intermetallic, NiCo and NiCu phases were identified in the bimetallic catalysts. The catalysts were studied in hydrodeoxygenation of lignocellulosic biomass-derived levulinic acid to γ-valerolactone (GVL) in a batch system by water as a solvent. Bimetallic, 10 wt.% Ni, and 10 wt.% Cu or Co containing fly ash zeolite catalysts showed higher catalytic activity than monometallic ones. Their selectivity to GVL reached 70-85% at about 100% conversion. The hydrogenation activity of catalysts was found to be stronger compared to their hydration ability; therefore, the reaction proceeds through formation of 4-hydroxy pentanoic acid as the only intermediate compound.

Effect of calcium on enhanced carbon capture potential of coal fly ash zeolites. Part II: a study on the adsorption mechanisms.

Coal fly ash zeolites (CFAZs) of type X with low (Na-X) and medium (Na-Ca-X) content of calcium were synthesized by alkaline conversion of lignite coal fly ash generated by combustion of lignite with lower and higher limestone amounts, extracted from different coal deposits and burned in separate thermal power plants. The concentration and state of Ca in the zeolites were investigated by energy dispersive X-ray (EDX) analysis and X-ray photoelectron spectroscopy (XPS). CFAZs Na-Ca-X with a medium Ca-content were found to outperform their lower calcium counterparts Na-X in terms of carbon capture capacity. This provoked our research interest in elucidating the role of Ca in the CO2 retaining mechanism. CFAZs Na-X and Na-Ca-X were studied in consecutive dynamic adsorption cycles, after thermal regeneration at a temperature of 80 °C, at which only the physically adsorbed CO2 molecules can be released. Desorption was investigated by thermogravimetric TG-DTG analyses over a wide temperature range. In situ Fourier-transform infrared (FTIR) spectroscopy was performed to elucidate the structural features of Na-X and Na-Ca-X CFAZs and the types of their accessible adsorption sites. It was found that the role of Ca is to increase the number of accessible Na+ cations in SII and SIII positions in the zeolites where they can simultaneously adsorb two CO or CO2 molecules, which benefits their adsorption capacity. This study raises an issue on coal ash classification for the synthesis of zeolites with carbon capture applications.

Comparative studies of carbon capture onto coal fly ash zeolites Na-X and Na-Ca-X.

The combustion of coal in Thermal Power Plants generates fine dust particles (coal fly ash, CFA), which are collected from the flue gas streams and deposited as solid wastes. One of the technologically reliable solutions for utilization of CFA is its alkaline conversion into zeolites. The present study focuses on the influence of calcium content in CFA on the chemical and phase composition, morphology and surface properties of coal fly ash zeolites. Comparative studies of the capacity of zeolites of Na-X and Na-Ca-X types from coal fly ash to capture carbon emissions under static and dynamic conditions have been performed. The present study answers a key question from a practical point of view, how does moisture in flue gases affect the adsorption of carbon dioxide on zeolites. The development of efficient adsorbents from CFA with varying composition will contribute to a number of environmental benefits and to the development of efficient CO2 capture technologies in the context of the circular economy.

Acetone-Sensitive Thin Films Comprising Coal Fly Ash Na-X Zeolites and Sol-Gel Nb2O5 Matrix.

In this study, thin composite films of a sol-gel Nb2O5 matrix doped with coal fly ash Na-X zeolites were deposited by the spin-coating method. Fly ash of lignite coal collected from the electrostatic precipitators of one of the biggest TPPs in Bulgaria was used as a raw material for obtaining zeolites. Zeolite Na-X was synthesized by ultrasonic-assisted double stage fusion-hydrothermal alkaline conversion of coal fly ash. In order to improve the optical quality and sensing properties of the deposited thin films, synthesized zeolites were wet-milled for 60, 120, and 540 s prior to film deposition. The surface morphology of zeolite powders was studied both by scanning electron microscopy and transmission electron microscopy, while their porosity was investigated by N2-physisorption. Refractive index, extinction coefficient, and thickness of the films were determined through fitting of their reflectance spectra. The sensing ability of thin films towards acetone vapors was tested by measuring the reflectance spectra prior to and during exposure to the analyte, and the change in the reflection coefficient ∆R of the films was calculated. The influence of milling time of zeolites on the sensing and optical properties of the films was assumed and confirmed.

Progress in the Utilization of Coal Fly Ash by Conversion to Zeolites with Green Energy Applications.

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.

Studies on non-modified and copper-modified coal ash zeolites as heterogeneous catalysts for VOCs oxidation.

The present study is aimed at investigations on the catalytic activity for total oxidation of volatile organic compounds (VOCs), such as toluene, acetone, n-hexane and dichlorobenzene onto zeolite-like materials synthesized from coal fly ash (FA) directed to development of an economically efficient approach for degradation of VOCs. Fly ash zeolites (FAZ) were prepared by alkaline conversion of FA collected from Thermal Power Plants supplied with lignite coal from "Maritza-East" basin in Bulgaria. Different synthesis procedures double stage fusion-hydrothermal activation, fusion-atmospheric crystallization and atmospheric aging were applied. The synthesis products were identified by X-ray diffraction, and were assigned to zeolite Na-X. Scanning electron microscopy images reveal submicron dimensions of the composing crystallites. Nitrogen adsorption/desorption measurements reveal a mixed micro-mesoporous structure and specific surface area between 116 and 396 m2/g for the obtained FAZ. Relationships between surface properties, iron content and the catalytic activity of FAZ were investigated and discussed. Copper-modified fly ash zeolites (Cu-FAZ) were prepared by incipient wetness impregnation technique with copper acetylacetonate. The loading of 5 wt. % copper on the zeolite samples was achieved. The catalytic activity of FAZ and Cu-FAZ in the total oxidation of model VOCs mixture containing n-hexane, acetone, toluene, 1,2 dichlorobenzene was evaluated.