Biomass-based production of trimellitic and trimesic acids

The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene.To reduce the dependence on the limited oil source,we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol(MPD),acrylate and crotonaldehyde as starting materials.The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate,flow aromatization over Pd/C catalyst,hydrolysis and catalytic aerobic oxidation(60%overall yield).The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO_(2)H.Crotonaldehyde can also participate in the reaction,followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54%overall yield.Life cycle assessment implies that compared to conventional fossil process,our biomass-based routes present a potential in reducing carbon emissions.

Synthesis of jet fuel additive with cyclopentanone

A new route was developed for the synthesis of renewable decalin with cyclopentanone which can be derived from lignocellulose.It was found that 1,2,3,4,5,6,7,8-octahydronaphthalene could be selectively produced by the hydrogenation/dehydration/rearrangement of [1,1-bi(cyclopentylidene)]-2-one(i.e.the selfaldol condensation product of cyclopentanone) over a dual-bed catalyst system.Among the investigated catalysts,the Ru/C and Amberlyst-15 resin exhibited the highest activities for the hydrogenation of [1,1-bi(cyclopentylidene)]-2-one to [1,1-bi(cyclopentan)]-2-ol and the dehydration/rearrangement of [1,1-bi(cyclopentan)]-2-ol to 1,2,3,4,5,6,7,8-octahydronaphthalene,respectively.Using Ru/C and Amberlyst-15 resin as the first bed and the second bed catalysts,1,2,3,4,5,6,7,8-octahydronaphthalene was directly produced in high carbon yield(83.7%) under mild conditions(393 K,1 MPa).After being hydrogenated,the1,2,3,4,5,6,7,8-octahydronaphthalene was converted to decalin which can be used as additive to improve the thermal stability and volumetric heat value of jet fuel.