Catalysis Today, Vol.375, 132-144, 2021
Processes of catalytic oxidation for the production of chemicals from softwood biomass
Two alternative routes of softwood catalytic oxidative fractionation to cellulose products and fine chemicals are assessed. We suggested to use the process of larch wood peroxide oxidation in the medium acetic acid - water at temperatures 70-100 degrees C in the presence of soluble catalyst (NH4)(6)Mo7O24 to produce microcrystalline cellulose (35.0 wt% on wood), microfibrillated cellulose (7.5 wt% on wood) or nanocrystalline cellulose (3.7 wt% on wood) and low molecular weight organic compounds (20 wt% on wood). The developed process reduces the number of technological stages and increase an environmentally safety of nanocelluloses production from wood, compared to traditional technologies. Another suggested process of softwood (pine and larch) fractionation to vanillin (up to 4.7 wt% on wood) and cellulose (up to 34.6 wt% on wood) is based on wood oxidation by oxygen in water-alkaline medium at temperatures 160-180 degrees C in the presence of suspended catalyst Cu(OH)(2). The further acid conversion of cellulose by 2 % H(2)SO(4)at 180 degrees C produces levulinic acid with the yield up to 9.7 wt % on wood. The integration of the processes of dihydroquercetin and arabinogalactan extraction isolation from larch wood, oxidation of extracted wood by oxygen to vanillin and cellulose in the presence of catalyst Cu(OH)(2), acid catalyzed conversion of cellulose to levulinic acid and arabinogalactan hydrolysis over solid acid catalyst to arabinose and galactose leads to an increase in the number of target products. FTIR, XRD, SEM, AFM, solid state C-13 CP/MAS and chemical methods were used for characterization of cellulose products. Organic compounds were identified by GC, HPLC and GC-MS methods. The two alternative schemes of larch wood catalytic oxidative biorefinery to produce nanocelluloses and fine chemicals have been developed.