An efficient method for highly selective preparation of the high value-added benzyl alcohol (BOL) and benzaldehyde (BAL) from liquid-phase catalytic oxidation of toluene with molecular oxygen over CeO2-MnOx composite oxides...
Copper-containing mixed metal oxides are one of the most promising catalysts of selective catalytic oxidation of ammonia. These materials are characterized by high catalytic efficiency; however, process selectivity to dinitrogen is still an open challenge. The set of Cu-Zn-Al-O and Ce/Cu-Zn-Al-O mixed metal oxides were tested as catalysts of selective catalytic oxidation of ammonia. At the low-temperature range, from 250 °C up to 350 °C, materials show high catalytic activity and relatively high selectivity to dinitrogen. Samples with the highest Cu loading 12 and 15 mol.% of total cation content were found to be the most active materials. Additional sample modification by wet impregnation of cerium (8 wt.%) improves catalytic efficiency, especially N2 selectivity. The comparison of catalytic tests with results of physicochemical characterization allows connecting the catalysts efficiency with the form and distribution of CuO on the samples’ surface. The bulk-like well-developed phases were associated with sample activity, while the dispersed CuO phases with dinitrogen selectivity. Material characterization included phase composition analysis (X-ray powder diffraction, UV-Vis diffuse reflectance spectroscopy), determination of textural properties (low-temperature N2 sorption, scanning electron microscopy) and sample reducibility analysis (H2 temperature-programmed reduction).
Lignin, a complex aromatic polymer with different types of methoxylated phenylpropanoid connections, enables the sustainable supply of value-added chemicals and biofuels through its use as a feedstock. Despite the development of numerous methodologies that upgrade lignin to high-value chemicals such as drugs and organic synthesis intermediates, the variety of valuable products obtained from lignin is still very limited, mainly delivering hydrocarbons and oxygenates. Using selective oxidation and activation cleavage of lignin, we can obtain value-added aromatics, including phenols, aldehydes, ketones, and carboxylic acid. However, biorefineries will demand a broad spectrum of fine chemicals in the future, not just simple chemicals like aldehydes and ketones containing simple C = O groups. In particular, most n-containing aromatics, which have found important applications in materials science, agro-chemistry, and medicinal chemistry, such as amide, aniline, and nitrogen heterocyclic compounds, are obtained through n-containing reagents mediating the oxidation cleavage in lignin. This tutorial review provides updates on recent advances in different classes of chemicals from the catalytic oxidation system in lignin depolymerization, which also introduces those functionalized products through a conventional synthesis method. A comparison with traditional synthetic strategies reveals the feasibility of the lignin model and real lignin utilization. Promising applications of functionalized compounds in synthetic transformation, drugs, dyes, and textiles are also discussed.
AbstractThe selective oxidative conversion of seven representative fully characterized biomasses recovered as secondary feedstocks from the agroindustry is reported. The reaction system, known as the “OxFA process,” involves a homogeneous polyoxometalate catalyst (H8PV5Mo7O40), gaseous oxygen, p-toluene sulfonic acid, and water as solvent. It took place at 20 bar and 90 °C and transformed agro-industrial wastes, such as coffee husks, cocoa husks, palm rachis, fiber and nuts, sugarcane bagasse, and rice husks into biogenic formic acid, acetic acid, and CO2 as sole products. Even though all samples were transformed; remarkably, the reaction obtains up to 64, and 55% combined yield of formic and acetic acid for coffee and cocoa husks as raw material within 24 h, respectively. In addition to the role of the catalysts and additive for promoting the reaction, the influence of biomass components (hemicellulose, cellulose and lignin) into biogenic formic acid formation has been also demonstrated. Thus, these results are of major interest for the application of novel oxidation techniques under real recovered biomass for producing value-added products.