Plant-based biomass is an abundant feedstock source to meet the rapidly increasing global demand for chemicals. New chemistries and resource-efficient catalytic technologies that conserve feedstock and energy are needed to produce petrochemical equivalents from this distributed feedstock. In this talk, we present new oxidation concepts that admit these attributes. In one example, we discuss spray oxidations of p-xylene and 5-hydroxymethylfurfural to produce terephthalic acid and 2,5-furandicarboxylic acid, respectively, employing the homogenous Co/Mn/Br catalytic system in acetic acid medium. The combination of increased gas-liquid mass transfer area and short residence times in the spray reactor allows high yields of polymer-grade products in one step and reduces substrate burning compared to the conventional stirred reactor that requires a second hydrogenation step to purify the crude product. In another example, we show how liquid CO2 is an effective ozone carrier for performing ozonolysis of fatty acid methyl esters. Ozone is a potent oxidant that is stable in liquid CO2 with solubilities greater than in CCl4. Further, the presence of dense CO2 (a flame retardant) in the vapor phase eliminates flammability. Rapid, safe and selective ozonolysis is demonstrated by mixing ozone-laden liquid CO2 with methyl oleate in a continuous reactor with short residence times. The secondary ozonides are thermally decomposed in a subsequent stirred reactor to yield nonanal and nonanoic acid. In the final example, a spray ozonolysis concept is demonstrated for the valorization of lignin from various sources to yield valuable aromatic monomers.

Intensified oxidative processes for biomass conversion to chemicals

253rd National Meeting (2017)

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