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SSCI-VIDE+CDFA+LDJ:FRA; International audience; In the present work, a kinetic study and optimization of the process of spruce wood peroxide oxidation in “acetic acid–water” medium in the presence of suspended TiO2 catalyst at temperatures 70–100 °C were accomplished for the first time. The effect of wood species and organic solvent nature on the features of the processes of catalytic peroxide fractionation of wood biomass on microcrystalline cellulose and soluble organic products from lignin and hemicelluloses is described. Solid products of wood peroxide oxidation were characterized by FTIR, XRD, SEM, solid state 13C CP-MAS NMR and soluble products were identified by GC–MS. The experimental optimization of the process of birch wood oxidation by oxygen in “water–alkaline” medium in the presence of suspended Cu(OH)2 catalyst was carried out at temperature range 160–180 °C. The scheme of biorefinery of birch wood, based on catalytic oxidative fractionation of wood biomass with the production of pentosans, vanillin, syringaldehyde and levulinic acid was developed. The resulting products are in demand in many areas, including food, pharmaceutical, chemical, cosmetic industries, synthesis of new functional and biodegradable polymers.

International audience; 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 °C in the presence of soluble catalyst (NH4)6Mo7O24 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 °C in the presence of suspended catalyst Cu(OH)2. The further acid conversion of cellulose by 2 % H2SO4at 180 °C produces levulinic acid with the yield up to 9.7 wt % on wood.he 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 13C 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.

A new method to obtain cellulose sulfates from available and inexpensive raw material—aspen wood was developed. This method integrates catalytic peroxide delignification and sulfamic acid sulfation stages. Solvents such as acetic acid and water were used for isolation of pure cellulose by wood peroxide delignification with TiO2 catalyst. Low-aggressive and less-toxic sulfating agent—sulfamic acid–urea mixture was used to obtain cellulose sulfates.

Results of the study on green valorization of hardwood biomass into valuable chemicals with the use of solid catalysts were described. The heterogeneous catalytic processes of hemicelluloses and cellulose hydrolysis, wood oxidative fractionation and lignin depolymerization in supercritical spirits are suggested to employ for the green biorefinery of hardwood to xylose, pure cellulose, glucose, alcohols and liquid hydrocarbons.

A kinetic study and optimization of pine wood peroxide fractionation in the medium acetic acid–water over TiO2 catalyst were accomplished for the first time. Kinetic regularities and the product composition of green processes of catalytic peroxide fractionation of softwood (pine, abies, larch) and hardwood (aspen, birch) over 1 wt% TiO2 catalyst in the acetic acid–water medium were compared at the temperature range 70–100 °C. For all type of wood, the processes of peroxide delignification are described by the first order equations and their activation energies are varied at the range 76–94 kJ/mol. According to FTIR, XRD, SEM, NMR data, the cellulosic products of peroxide delignification have a structure similar to microcrystalline cellulose regardless of the nature of wood. Soluble products are presented by organic acid and monosaccharides. The scheme of green biorefinery of pine wood based on extractive-catalytic fractionation of wood biomass on microcrystalline cellulose, hemicelluloses, aromatic and aliphatic acids, monosaccharides, turpentine and rosin was developed. Green and non-toxic reagents and solid catalyst are used in the developed scheme of biorefinery.

Two ways of catalytic depolymerization of native and isolated wood lignins are described: the peroxide delignification of hardwood (aspen, birch) and softwood (abies) in the medium of acetic acid – water over TiO2 catalyst and the thermal dissolution of organosolv lignins (ethanol-lignin and acetone-lignin) in supercritical alcohols (ethanol and butanol) over solid Ni-containing catalysts. The catalyst TiO2 in rutile modification has the higher activity in wood peroxide delignification at 100 °C as compared to TiO2 in anatase modification. The results of kinetic studies and optimization of the processes of peroxide depolymerization of hardwood (aspen, birch) and softwood (abies) lignins in the medium of acetic acid – water over catalyst TiO2 (rutile) at mild conditions (≤100 °C, atmospheric pressure) are compared. The catalyst TiO2 initiates the formation of OH and OOH radicals from H2O2 which promote the oxidative fragmentation of wood lignin. In this case, the peroxide depolymerization of softwood lignin, constructed from phenylpropane units of guaiacyl-type proceeds more difficult than the hardwood lignins, mainly containing syringyl-type units. The solid and soluble products of peroxide catalytic delignification of wood under the optimized conditions were studied by FTIR, XRD, GC–MS and chemical methods. Regardless of the nature of wood the cellulosic products have a structure similar to microcrystalline cellulose. The soluble products mainly consist of monosaccharides and organic acids. Aromatic compounds are present only in a low amount which indicates the oxidative degradation of aromatic rings of lignin phenylpropane units under the used conditions of wood catalytic delignification. The processes of thermal dissolution of acetone-lignin and ethanol-lignin from aspen-wood in supercritical ethanol and butanol over Ni-containing catalyst (NiCu/SiO2, NiCuMo/SiO2) are compared. The composition, structure and thermal properties of organosolv lignins were studied with the use of FTIR, GPC, 1H – 13C HSQC NMR, DTA and elemental analysis. The influence of a composition of Ni-containing catalyst on the thermal conversion in supercritical butanol and ethanol of ethanol-lignin and acetone-lignin was established. The highest conversion of lignins (to 93% wt.) in supercritical alcohols and the highest yield of liquid products (to 90% wt.) were achieved at 300 °C in the presence of catalyst NiCuMo/SiO2. Scheme of green biorefinery of wood based on the use of non-toxic and low-toxic reagents (H2O2, H2O, acetic acid, ethanol, butanol) and solid catalysts (TiO2, NiCuMo/SiO2) is suggested.

The first green biorefinery of larch wood based on the fractionation of biomass into dihydroquercetin (DHQ), arabinogalactan (AG), microcrystalline cellulose (MCC) and soluble lignin (SL) is reported. The new green method of one-step isolation of DHQ and AG from larch wood by ethanol–water solution was developed. The first results of kinetic studies and optimization of the process of extracted larch wood peroxide fractionation into MCC and SL in acetic acid–water medium in the presence of green TiO2 catalyst are described. The products obtained from larch wood were characterized by FTIR, NMR, XRD, AFM and chemical methods. The scheme of larch wood biorefinery is suggested which integrates the developed processes of woody biomass fractionation into DHQ, AG, MCC and SL. All developed methods use non-toxic and less-toxic reagents, such as water, ethanol, hydrogen peroxide and acetic acid.