Glycerolysis of Crude Methyl Esters with Crude Glycerol from Biodiesel Production

Glycerolysis of crude fatty acid methyl esters (FAME) with crude glycerol derived from biodiesel production was performed. The reaction was accomplished at temperatures ranging between 160 and 200 °C and molar ratios of FAME to glycerol ranging between 1.5 and 3.0. Increasing the temperature improved the formation rate of monoglycerides (MG) and diglycerides (DG). However, increasing both the temperature and the molar ratio of glycerol to FAME diminished the formation of MG. Best results (43 % MG and 26 % DG in 10 min) were obtained at 200 °C using the lowest concentration of glycerol. The effects of soap and NaOH present in crude glycerol were controlled by carrying out the reaction with pure glycerol. In comparison with NaOH-catalyzed reactions, soap-catalyzed reactions resulted in a slower formation rate of products. However, soap-catalyzed reactions were less prone to secondary reactions, affording maximum yields of MG and DG, which were higher than those obtained with NaOH-catalyzed reactions at 180 and 200 °C.     

One‐Pot Homogeneous and Heterogeneous Oxidation of Glycerol to Ketomalonic Acid Mediated by TEMPO

Glycerol, an increasingly abundant by‐product of biodiesel production, is selectively converted to ketomalonic acid in one pot at pH 10 using NaOCl as regenerating oxidant in water at 2 °C in the presence of catalytic Br⁻ along with the radical TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl). The reaction can also be conducted at completion over a sol‐gel silica glass doped with the nitroxyl radical. Considering the stability and versatility of such doped glasses, these materials show real promise as reusable metal‐free catalysts for the conversion of a readily available and renewable biofeedstock into a highly valued compound.     

Enzymatic Synthesis of Biodiesel from Transesterification Reactions of Vegetable Oils and Short Chain Alcohols

Biodiesel synthesis by alcoholysis of three vegetable oils (soybean, sunflower and rice bran) catalyzed by three commercial lipases (Novozym 435, Lipozyme TL-IM and Lipozyme RM-IM), and the optimization of the enzymes stability over repeated batches is described. The effects of the molar ratio of alcohol to oil and the reaction temperature with methanol, ethanol, propanol and butanol were also studied. All three enzymes displayed similar reaction kinetics with all three oils and no significant differences were observed. However, each lipase displayed the highest alcoholysis activity with a different alcohol. Novozym 435 presented higher activity in methanolysis, at a 5:1 methanol:oil molar ratio; Lipozyme TL-IM presented higher activity in ethanolysis, at a 7:1 ethanol:oil molar ratio; and Lipozyme RM-IM presented higher activity in butanolysis, at a 9:1 butanol:oil molar ratio. The optimal temperature was in the range of 30–35 °C for all lipases. The assessment of enzyme stability over repeated batches was carried out by washing the immobilized enzymes with different solvents (n-hexane, water, ethanol, or propanol) after each batch. When washing with n-hexane, approximately 90% of the enzyme activity remained after seven synthesis cycles.     

A Novel and Efficient Synthesis of Tocopheryl Quinones by Homogeneous and Heterogeneous Methyltrioxorhenium/Hydrogen Peroxide Catalytic Systems

A convenient and efficient application of heterogeneous poly(4‐vinylpyridine), poly(4‐vinylpyridine N‐oxide), and polystyrene/methylrhenium trioxide systems for the selective oxidation of tocopherols and tocopherol derivatives to the corresponding ortho‐ and para‐tocopherylquinones is described. Environment friendly, easily available, and low‐cost hydrogen peroxide (H₂O₂) was used as the oxygen atom donor. The antiviral activity of the newly synthesized tocopherylquinones and their parent tocopherols against influenza A virus is also reported. On the basis of the biological assay, the activity of tocopherols against influenza virus is higher than that showed by the corresponding tocopherylquinones, thus suggesting, for the first time, a drawback effect of the oxidative metabolism on the antiviral activity of these compounds.     

Detergency of Vegetable Oils and Semi‐Solid Fats Using Microemulsion Mixtures of Anionic Extended Surfactants: The HLD Concept and Cold Water Applications

In spite of the increasing interest in cold temperature detergency of vegetable oils and fats, very limited research has been published on this topic. Extended surfactants have recently been shown to produce very promising detergency with vegetable oils at ambient temperature. However, the excessive salinity requirement (4–14 %) for these surfactants has limited their use in practical applications. In this work, we investigated the mixture of a linear C₁₀–18PO–2EO–NaSO₄ extended surfactant and a hydrophobic twin‐tailed sodium dioctyl sulfosuccinate surfactant for cold temperature detergency of vegetable oils and semi‐solid fats. Four vegetable oils of varying melting points (from ?10 to 28 °C) were studied, these were canola, jojoba, coconut and palm kernel oils. Anionic surfactant mixtures showed synergism in detergency performance compared to single surfactant systems. At temperatures above the melting point, greater than 90 % detergency was achieved at 0.5 % NaCl. While detergency performance decreased at temperatures below the melting point, it was still superior to that of a commercial detergent (up to 80 vs. 40 %). Further, results show that the experimental microemulsion phase behaviors correlated very well with predictions from the hydrophilic–lipophilic deviation concept.     

One‐Pot/Four‐Step/Palladium‐Catalyzed Synthesis of Indole Derivatives: The Combination of Heterogeneous and Homogeneous Systems

One‐pot, four‐step syntheses of indoles using both solid‐supported heterogeneous and homogeneous palladium catalysts and reagents were carried out. Such a combination of these two‐phase catalysts and reagents causes a dramatic increase in yield, and it is a simple process. The presented methodology is effective for four‐step reactions to provide various functionalized indoles.