Productive sugar isomerization with highly active Sn in dealuminated β zeolites

The availability of glycerol is rapidly increasing due to the expanding biodiesel industry, which produces this polyol as the main waste material. Several value-added chemicals have been synthesized using glycerol as a feedstock; however, the conversion of glycerol to lactic acid has been investigated to a lesser extent despite the numerous and novel uses of lactic acid. We report a family of iridium complexes as the first homogeneous catalysts for the conversion of glycerol to lactic acid. These have higher activity and selectivity than the previously reported heterogeneous systems. In addition, hydrogen gas is generated as a useful byproduct. Unlike prior systems, the reactions can be performed in air, under mild conditions and without solvent. Our method has even been applied to samples of crude glycerol waste derived from the biodiesel industry without prior purification, albeit with somewhat lower activity while maintaining the same high selectivity.

/pdf/efficient-selective-and-atom-economic-catalytic-conversion-4urczvirte.pdf

Efficient selective and atom economic catalytic conversion of glycerol to lactic acid

Lewis acid Snβ-type zeolites with varying amounts of Bronsted acid Al in the framework were synthesized using a simple two-step procedure comprising partial dealumination of β zeolite under action of acid, followed by grafting with SnCl4·5H2O in dry isopropanol. Characterization of the thus-prepared Al-containing Snβ (Sn/pDeAlβ) zeolites with ICP, (pyridine probed) FTIR, and 27Al MAS NMR demonstrates the presence of Bronsted acid framework AlIII. Tetrahedral Lewis acidic SnIV is present, as ascertained by a combination of techniques such as EPMA, 119Sn Moβbauer, XPS, (pyridine probed) FTIR, and UV–vis. A closed SnIV configuration was implied by comparing of 119Sn solid-state MAS NMR and deuterated acetonitrile probed FTIR spectra with literature. The catalytic activity of the Al-containing Snβ was tested for the conversion of 1,3-dihydroxyacetone (DHA) into ethyl lactate (ELA), proceeding via pyruvic aldehyde (PAL). Despite the difference in synthesis between the classic hydrothermal Snβ reference and Sn/...

Cooperative Catalysis for Multistep Biomass Conversion with Sn/Al Beta Zeolite

Heterogeneous catalysis for bio-based polyester monomers from cellulosic biomass: advances, challenges and prospects

Polylactic acid (PLA) is a very promising biodegradable, renewable, and biocompatible polymer. Aside from its production, its application field is also increasing, with use not only in commodity applications but also as durables and in biomedicine. In the current PLA production scheme, the most expensive part is not the polymerization itself but obtaining the building blocks lactic acid (LA) and lactide, the actual cyclic monomer for polymerization. Although the synthesis of LA and the polymerization have been studied systematically, reports of lactide synthesis are scarce. Most lactide synthesis methods are described in patent literature, and current energy-intensive, aselective industrial processes are based on archaic scientific literature. This Review, therefore, highlights new methods with a technical comparison and description of the different approaches. Water-removal methodologies are compared, as this is a crucial factor in PLA production. Apart from the synthesis of lactide, this Review also emphasizes the use of chemically produced racemic lactic acid (esters) as a starting point in the PLA production scheme. Stereochemically tailored PLA can be produced according to such a strategy, giving access to various polymer properties.

Lactide Synthesis and Chirality Control for Polylactic acid Production

Bridging racemic lactate esters with stereoselective polylactic acid using commercial lipase catalysis

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Bridging racemic lactate esters with stereoselective polylactic acid using commercial lipase catalysis