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1.
ChemistryOpen ; 12(2): e202200247, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36722831

RESUMO

The conversion of biomass faces the challenge of mass and heat transfer, as well as the exertion of heterogeneous catalyst, because raw biomass exists usually in solid state. In this work, the simultaneous transformation and dissolution of the three main components (hemicellulose, cellulose, lignin) in corn straw were achieved in ethanol/ valerolactone (GVL)/H2 O (10 : 10 : 40, v/v/v) co-solvent system. With the assistance of AlCl3 ⋅ 6H2 O, the conversion of hemicellulose, lignin and cellulose was >96 % at 170 °C. The conversion of solid biomass into fluid, overcoming the mass transfer restrictions between solid biomass and solid catalysts, provides new raw materials to further upgrading. H2 O could penetrate inside the crystalline cellulose to swell even dissolve it, while ethanol and GVL acted as media to dissolve especially the G unit in lignin. The H+ derived from AlCl3 ⋅ 6H2 O hydrolysis could break the linkages of lignin-hemicellulose and glycosidic bond in saccharides, and aluminum chloride promoted the next degradation of polysaccharides to small molecules. Consequently, as high as 33.2 % yield of levulinic acid and 42.2 % yield of furfural were obtained. The cleavage of ß-O-4 and Cß -Cγ bonds in lignin produced large amounts of lignin-derived dimers and trimers. The total yield of monomeric phenols is up to 8 %.

2.
ChemSusChem ; 15(23): e202201537, 2022 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-36161773

RESUMO

Glycerol valorization towards high-value chemicals is of particular importance to increase the value chain of biodiesel production. In this study, the catalytic activity of a series of cheap Cu-based catalysts for glycerol conversion is investigated. Cu supported on activated carbon (AC, obtained through carbonization of coconut shell) exhibits outstanding catalytic activity for the selective conversion of glycerol into glycolic acid (GcA) in O2 atmosphere, affording up to 68.3 % GcA yield. The combination of experimental results with theoretical calculations reveals that glyceraldehyde is the key reaction intermediate. The high specific surface area and surface oxygenated groups of AC enable the formation of CuO nanoparticles with small size and uniform dispersion. In addition, the surface oxygen vacancy on Cu/AC might help to activate reaction intermediates, and the electron transfer from Cu to AC facilitates the oxidation of glycerol to GcA. Cu loaded onto AC also significantly inhibits C-C breakage to generate formic acid as a byproduct. This work might aid the development of approaches for glycerol application and afford profitable possibilities for sustainable biodiesel.


Assuntos
Carvão Vegetal , Glicerol
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