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Sulfation of birch wood xylan in 1,4-dioxane by sulfamic acid in the presence of urea at 90 and 100 °C was studied for the first time. The effect of the duration of xylan sulfation on the yield of xylan sulfates and the sulfur content in them was studied. It was found that the sulfur content in the obtained xylan sulfates increases from 12.5 to 17.5 wt% with an increase in the duration of sulfation from 2 to 4 hours. The structure of initial and sulfated xylan was studied by FTIR and NMR spectroscopy. The ease of purification of the obtained xylan sulfates from 1,4-dioxane in comparison with the purification of xylan sulfates obtained by sulfation in pyridine and N, N‑dimethylformamide is an advantage of the proposed method of xylan sulfation

γ-Valerolactone (GVL) is a valuable chemical compound known as a platform molecule. It is considered as an intermediate product for the synthesis of chemical compounds with high added value, components of motor fuels, and biopolymers. GVL is well established as an environmentally safe solvent, fuel additive, flavoring, and nutritional supplement. This review summarizes the latest advances in the development of catalytic ways of GVL synthesis from levulinic acid (LA), alkyl levulinates (ALs), and carbohydrates and plant polymers. Special attention is given to heterogeneous catalysts based on metals and metal oxides, which are more promising for practical application. Proposed mechanisms of the processes are considered in detail, and the prospect of using hydrogen-donor solvents in the processes of GVL production is discussed. Catalysts demonstrating the best catalytic properties are compared from the viewpoint of their productivity, an important parameter for industrial catalysis.

For the first time, tannin-lignin-formaldehyde and tannin-lignin-furfuryl organic gels were obtained on the basis of larch bark tannins and hydrolysis lignin by sol-gel condensation with formaldehyde and furfuryl alcohol. Their physico-chemical properties were studied by varying the content of lignin (from 5 to 30 wt%) and a fixed mass ratio of polyphenolic substances to the crosslinking reagent (1 : 1.5). With an increase in the lignin content the density of tannin-lignin formaldehyde gels decreases from 0.83 to 0.53 g/ cm3, and that of tannin-lignin-furfuryl gels is from 0.32 to 0.14 g / cm3. According to the FTIR data, the structures of tannin-lignin-formaldehyde and tannin-lignin-furfuryl gels are formed by aromatic fragments cross-linked with methylene and methylene-ether bridges. Scanning electron microscopy shows that the addition of appropriate amounts of lignin to tannins (up to 10 wt% when using formaldehyde and up to 20 wt% when using furfuryl alcohol) promotes the formation of gels with a more developed porous structure. In the case of tannin-lignin-formaldehyde gel, the specific surface area and sorption of methylene blue are 12 m2 / g and 43 mg / g and for tannin-lignin-furfuryl gel – 72 m2 / g and 114.5 mg/g, respectively. It was found that an increase in the lignin content in the gel composition over 20 wt.% is accompanied by the phase localization of lignin (precipitation), which reduces the strength of the resulting gel and reduces its specific surface area.

The analysis of the latest publications on the use of hydrolytic lignin, which is a large-tonnage waste of wood chemical processing, was carried out. In its original form, the hydrolytic lignin is used as fuel, fuel briquettes and pellets, binders and adhesives, organic fertilizers, fillers and enterosorbents. The processing of hydrolytic lignin by chemical and thermochemical methods allows to significantly expand the range of valuable products obtained from it. They are used in chemical, oil and gas and construction industries, metallurgy and other areas. Hydrolytic lignin is most widely used for the production of carbon sorbents. Recently, methods of thermochemical processing of lignin into porous carbon materials with the required texture and strength characteristics as well as into valuable organic products have been developed

γ-Valerolactone (GVL), which is a valuable chemical compound and a platform molecule, is considered as an intermediate product for the synthesis of chemical compounds with high added value, components of motor fuels and biopolymers. GVL is successfully used as an environmentally friendly solvent, fuel additive, fragrance and food additive. This review summarizes recent advances in the development of catalytic methods for the production of GVL from levulinic acid (LA), alkyl levulinates (AL), carbohydrates and vegetable polymers. Particular attention is paid to heterogeneous catalysts based on metals and metal oxides, which are more promising for practical application. The proposed mechanisms of processes are considered in detail, and prospects of using hydrogen-donor solvents in the production of GVL are discussed. Catalysts with the best catalytic performance were compared in terms of their productivity, which is an important parameter for industrial catalysis.

A comparison of IR spectra and molecular weight distribution of arabinogalactan sulfates as sodium and ammonium salts obtained using various sulfating reagents was performed. According to the data, sulfated derivatives of arabinogalactan differ from each other in the nature of hydrogen bonds and molecular weight distribution. Using coagulological tests during activation of coagulation of platelet-poor human plasma in vitro, the anticoagulant properties of sulfated arabinogalactan derivatives in various salt forms differing in the preparation method, sulfation degree, and molecular weight were studied. It was found that the sample in the form of the sodium salt of sulfated arabinogalactan (SAG 1) with a sulfur content of 13.2 wt % and a polydispersity degree of 1.52 exhibited twofold greater anticoagulant activity than the sample in the form of the ammonium salt of sulfated arabinogalactan (SAG 2) with a sulfur content of 6.6 wt % and a polydispersity degree of 1.30. The antithrombin (aIIa) activity of the samples obtained by sulfation with a complex of pyridine and sulfuric anhydride (SAG 1) and a complex of sulfamic acid (SAG 2) was 23.42 ± 1.86 and 10.20 ± 1.50 U/mg, respectively; the value of the antifactor Xa activity of SAG 1 and SAG 2 was 2.13 ± 0.42 and 0.37 ± 0.08 U/mg; the aIIa/aXa ratio for SAG 1 and SAG 2 was 11 and 28, respectively. The antifactor Xa (aXa) activity of SAG, which is lower than that of unfractionated heparin (UFH), and a high aIIa/aXa activity ratio may contribute to less provocation of bleeding by SAG samples compared to UFH.

Lignin is a large-scale waste product of hydrolysis and the pulp-and-paper industries. The problem of lignin utilization is addressed by developing techniques for the comprehensive processing of wood biomass that are based on preliminary catalytic fractionation into its key components, which are subsequently used for obtaining target products. Hemicelluloses of larch wood are known to undergo effective depolymerization (~95 wt %) in ethanol at 250°C. Using hydrogen in combination with a catalyst enables us to increase the lignin conversion to 61 wt %, with 47 wt % of the cellulose left in the solid residue. The highest lignin conversion (67 wt %) is achieved using formic acid, but there is undesirable cellulose depolymerization (conversion, 66 wt %) under these conditions. The main monomer products of the catalytic conversion of lignin are 4-propenylguaiacol and 4-propylguaiacol. The content of 4-propenylguaiacol among the liquid products obtained using ethanol and formic acid as reducing agents can be as high as 36 and 33 rel %, respectively. The content of 4-propylguaiacol among the liquid products obtained using hydrogen grows to 33 rel % when a catalyst is used. This work describes the first study of the catalytic fractionation of larch wood in supercritical ethanol in the presence of the bifunctional 3%Ru/C catalyst containing acidic groups. The aim is to identify the effect of the catalyst and the nature of the hydrogen donor (ethanol, H2, or formic acid) on the yield and composition of the product.

The porous structure and sorption properties of carbon materials produced by thermochemical activation of the bast of birch bark with potassium hydroxide at 800°C have been studied. The effect of the amount of introduced KOH on the specific surface area of carbon materials obtained from bast was established. The selection of the optimal conditions for the preliminary carbonization of the bast was carried out, providing after thermal activation with KOH the formation of porous carbon materials with a specific surface of up to 2469 m2 g–1, a total pore volume of up to 1.085 cm3 g–1, a micropore volume of up to 0.84 cm3 g–1, and an average size pores less than 2.0 nm. It is shown that preliminary carbonization of bast at 500–580°С and subsequent activation with KOH at 800°С shifts the pore distribution in the resulting carbon materials towards smaller sizes (0.5–1.0 nm). It was found that carbon materials produced from heat-treated birch bast have a sorption activity for benzene, which exceeds the performance of foreign industrial carbon sorbents by 2.4 times and domestic active carbons of SKT-3 and SKT-10 grades by 3.4 times. Pre-carbonization of birch bast increases the yield of porous carbon materials by a factor of 3–4 compared to their yield when using untreated bast.

Experiments and calculations are used to determine the optimum parameters of the peroxide delignification of larch wood in the presence of MnSO4 catalyst that provides high yields of cellulose (44.3 wt %) with low residual lignin contents at a temperature of 100°C, an H2O2 content of 6 wt %, a CH3COOH content of 25 wt %, a LWR of 15, and a duration of 3 h The cellulose obtained under optimum conditions has a chemical composition of cellulose, 92.7 wt %; lignin, 0.6 wt %; and hemicellulose, 5.7 wt %. IRS and X-ray diffraction are used to determine that cellulose obtained from larch wood has a structure similar to that of industrial microcrystalline cellulose. The proposed catalytic approach allows cellulose to be obtained from larch wood with a minimal lignin content under mild conditions in one step and with a high yield, a degree of crystallinity of 0.8, and a crystallite size of 3.0 nm.

The regularities of thermocatalytic transformation of pine ethanol lignin in supercritical ethanol in the presence of catalysts NiCu/SiO₂ and NiCuMo/SiO2 in the temperature range 250–400 °C were established. The composition and structure of ethanol lignin, liquid and solid products of its conversion were studied by methods of elemental analysis and gel-permeating chromatography (GPC). The composition of gaseous products – by method of gas chromatography. At the process temperature of 250 °C the catalysts do not have a significant effect on conversion of ethanol lignin. The maximal yield of liquid products (83.5 wt. %) was obtained at temperature 300 °C in the presence of catalyst NiCuMo/SiO₂ containing 8.8 wt. % of molybdenum. At temperature 350 °C NiCu/SiO₂ and NiCuMo/SiO2 catalysts contribute to the almost complete conversion of ethanol lignin into liquid and gaseous products, and the yield of solid products does not exceed 1 wt. %. In liquid products of catalytic conversion there is a decrease in the atomic ratio of O/C and the increase of H/C atomic ratio as compared to initial ethanol lignin due to catalytic intensification of reactions of deoxygenation and hydrogenation of lignin and products of its depolymerization. According to GPC data on the curves of molecular mass distribution (MMD) of liquid products of thermocatalytic conversion of ethanol lignin at 300 °C there are peaks with highs at 160 and 380 Da, probably related to guiacyle monomers and dimmers, respectively. From the comparison of MMD of liquid products obtained by ethanol lignin depolymerization at 300 °C over catalysts NiCu/SiO₂ and NiCuMo/SiO₂ it follows, that the introduction of molybdenum in the catalyst promotes the formation of monomeric guaiacyl products

The process of abies ethanol lignin sulfation with sulfamic acid in 1,4-dioxane medium in the presence of urea was optimized by calculation methods. The influence of such factors, as the ratio of lignin/sulfating complex (L/SC), temperature and time of the sulfation process on the sulfur content in the resulting sulfated ethanol lignin and its yield, has been established. The variance analysis of the obtained mathematical models testifies their good predictive properties. The optimal conditions of abies ethanol lignin sulfation process, which provide the formation of water-soluble sulfated lignin with a high yield (to 100 % wt.) and sulfur content (up to 7.9 % wt.), have been established. They are: temperature of 95-100 °C, the ratio L/SC 1:2,3-1:2:9 and the time of the process 119-137 minutes

The sulfation of ethanol lignin of abies wood by sulfamic acid–urea mixture in N,N-dimethylformamide (DMF) medium was studied for the first time. The effect of the duration of lignin sulfation process on the yield and sulfur content in resulted lignin sulfates was studied. It was shown that the reaction of ethanol lignin sulfation begins and ends in a homogeneous medium. At temperature 100 °C, the sulfur content in lignin varies from 5.4 to 6.8% mass, depending on the process time. The introduction of sulfate groups into the lignin structure was confirmed by FTIR and 2D NMR spectroscopy. It was found that both alcohol and phenolic hydroxyl groups of lignin enter the sulfation reaction. The molecular weight distribution of sulfated ethanol lignin was determined by gel permeation chromatography. The optimized method of synthesis allows to obtain sulfated ethanol lignin with low polydispersity (1.31) and narrow molecular weight distribution (3.25–3.75 kDa).

Lignin is a bulky waste of the hydrolysis and paper-pulp industry. To solve the problem of its utilization, approaches to deep processing of wood biomass are being developed; they are based on a preliminary catalytic fractionation of wood biomass into main components, which are processed into target products. For the first time, the reductive catalytic fractionation of larch was studied in a supercritical ethanol medium in the presence of 3%Ru/С bifunctional catalyst containing acid groups. The goal of the study was to reveal the effect of the catalyst and features of a hydrogen donor (ethanol, H2, formic acid) on the yields and composition of the products. It was shown that wood hemicelluloses efficiently (ca. 95 wt.%) depolymerize to ethanol at 250 °С. The use of hydrogen in the presence of the catalyst makes it possible to increase the conversion of lignin to 61 wt.% with retaining 47 wt.% cellulose in a solid residue. The maximum conversion of lignin equal to 67 wt.% was obtained in the presence of formic acid; however, the indicated conditions lead to undesirable depolymerization of cellulose (the conversion of 66 wt.%). The main monomeric products of lignin conversion on the catalyst are propenylguaiacol and propylguaiacol. In the liquid products obtained with ethanol and formic acid as the reductants, the content of propenylguaiacol reaches 36 and 33 rel.%, respectively. In the products obtained with hydrogen, the content of propylguaiacol increases to 33 rel.% in the presence of the catalyst.

The new method of producing of microfibrillated cellulose (MFC) from spruce wood was described. This method includes the stages of cellulose obtaining by peroxide delignification of wood in the medium “acetic acid-water-H2SO4 catalyst” and cellulose acid hydrolysis, ultrasonic treatment, and freeze drying. The structure of cellulosic products was studied by FTIR, XRD, SEM, AFM, dynamic light scattering methods. The particle size of final cellulosic products is characteristic of microfibrillated cellulose according to the TAPPI Standard WI 3021 classification. The particles of the MFC are characterized by a rather high surface charge, and its aqueous suspension showed a high colloidal stability for a long time. According to the AFM data the surface of the microfibrillated cellulose film is formed by homogeneous spherical particles with a diameter about 80 nm and does not contain external inclusions. The new method of obtaining MFC from spruce wood is less energy-consuming and more environmentally friendly compared to traditional technologies due to single-stage production of high quality cellulose without the use of sulfur- and chlorine containing delignifying agents, increased pressure and high water consumption.

Methods have been developed for the preparation of enterosorbents by treating crushed abies bark with the 1.5% aqueous of NaOH solution or by extraction with hexane. It was found that all obtained enterosorbents have good sorption properties with respect to gelatin and methylene blue. The highest sorption activity for methylene blue was shown by a sample, obtained by extraction of abies bark with hexane (97.0 mg/g), and for gelatin sorption activity – a sample, obtained by treatment of abies bark with alkali (225.0 mg/g). It was found that the enterosorbent, obtained by treatment of abies bark with alkali solution both at a dose of 0.15 g per kg of animal weight (g/kg) and at a dose of 0.20 g/kg and the enterosorbent, obtained by extraction of abies bark with hexane at a dose of 0.20 g/kg, have the highest efficiency for the treatment and prevention of acute experimental Escherichiosis. From the considered methods of obtaining enterosorbents from abies bark for the treatment and prevention of gastrointestinal infections of animals, it is recomended to use a method based on treatment of abies bark with alkalai solution and apply the drug in a dose of 0.15 g/kg

Carbon tannin-lignin-formaldehyde (TLF) gels were obtained for the first time by carbonization of organic xerogels synthesized by sol-gel condensation of formaldehyde with polyphenolic substances isolated from abies wood and bark – ethanol lignin and condensed tannins. The effect of the mass ratio of the tannins/lignin (T/L) components in the range 1:0 – 1:2 on the specific surface areas, porous volume, apparent density, and microstructure of carbon tannin-lignin-formaldehyde gels has been studied. It was found that the density of the carbon gels increases from 0.52 to 0.60 g/cm3 with a rises in the T/L ratio from 1:0 to 1:0.2 and 1:0.5 in the initial gel and then decreases to 0.20 and 0.13 g/cm3 with an increase in the lignin content to T/L ratios of 1:1 and 1:2, respectively. The study of the porous structure of carbon gels by the BET method showed that the carbon TLF gel obtained at a T/L ratio 1:2 is characterized by the highest specific surface area (538 m2/g). Using scanning electron microscopy, the structures of TF and TLF carbon gels have been studied. It has been established that the size of globular particles has a decisive influence on the structure of gels. The size of the globule particles increases with increasing of lignin content in the composition of the tannin-lignin-formaldehyde gel that leads to the formation of a less ordered structure of the carbon gel. The porous structure of TLF carbon gels obtained from abies polyphenolic substances can be regulated by varying the ratio of tannins:lignin. The obtained carbon gels can be used as sorbents and catalyst supports

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.

The new process of abies ethanol lignin sulfation by a low-toxic mixture of sulfamic acid and urea in 1,4-dioxane medium was optimized, and the structure of sulfated ethanol lignin was studied. The process of lignin sulfation is described by a first-order equation in the temperature range 70–100 °C. The value of the rate constants is weakly dependent on the ratios of lignin and sulfating complex (sulfamic acid–urea mixture). The activation energy of the sulfation process decreases from 11.5 to 7.5 kJ/mol with an increase in the content of the sulfating complex (SC). The optimal conditions for sulfation of abies ethanol lignin with a high yield of water-soluble sulfated lignin [(100% of mass) with sulfur content of 7.9%] were found: temperature 95–100 °C, L/SC ratio 1:2.3–1:2.9, time 2 h. The composition and structure of water-soluble sulfated ethanol lignin were determined by elemental analysis, FTIR spectroscopy, two-dimensional NMR spectroscopy and gel permeation chromatography. It was shown that only alcoholic OH groups of ethanol lignin react with sulfamic acid. Sulfated ethanol lignin has a higher molecular weight and a lower degree of polydispersity compared to the initial ethanol lignin.

The IR spectra and molecular mass distribution of arabinogalactan sulfates in the form of sodium and ammonium salts, obtained using various sulfating reagents, were compared. According to the obtained data, the sulfated derivatives of arabinogalactan differ from each other by the nature of the hydrogen bonds and the molecular weight distribution. Using coagulological tests at the activation of coagulation of platelet-poor human plasma, in vitro study of the anticoagulant properties of arabinogalactan sulfated derivatives in various salt forms differing in methods of preparation, degree of sulfation and molecular weight was conducted. It was established that the sample in the form of arabinogalactan sodium salt (SAG 1) with a sulfur content of 13.2 wt.% аnd a polydispersity degree of 1.52 showed 2 times more anticoagulant activity than the sample in the form of ammonium salt of arabinogalactan (SAG 2) with the sulfur content of 6.6 wt.% and the degree of polydispersity of 1.30. Antithrombin (aIIa) activity of samples obtained by sulfation with pyridine and sulfuric anhydride complex (SAG 1) and sulfamic acid complex (SAG 2) was, respectively, 23.42±1.86 and 10.20±1.50 U/mg; the anti-factor Xa activity of SAG 1 and SAG 2 was 2.13±0.42 and 0.37±0.08 U/mg; and the ratio aIIa/aXa for SAG1 and SAG 2 was 11 and 28, respectively. The less activity of antifactor Xa(aXA) of SAG as compared to unfractionated heparin (UFG) and higher rations of activities aIIa/aXa may contribute the less provocation of bleeding by SAG samples in the comparition with UFG.

The organic xerogels, prepared from tannins and ethanol lignins of the fir (Abies sibirica), were synthesized for the first time. The influence of the composition of initial mixture and pH on the characteristics of xerogels obtained by sol-gel condensation of formaldehyde with polyphenols of fir has been studied. The possibility of regulating the density and porosity of gels by varying of the concentration of ethanol lignin in the initial mixture was established. It was found that tannin-lignin-formaldehyde gel with low-density (0.11 g/cm3), and very high porosity (92%) is formed at a mass ratio tannins and lignins equal to 1. According to FTIR data, the process of xerogel formation is carried out by cross-linking due to the formation of carbon-carbon and alkyl ethers bonds. SEM method confirmed the formation of branched macromolecular structure of gels from interconnected spherical particles of different sizes. Thermogravimetric analysis demonstrates greater thermal stability of tannin-formaldehyde gels compared with the tannin-lignin-formaldehyde gels. The increase of lignin concentration in gels more than 50–65% (by the mass) reduced the temperature of their intensive mass loss on 23–63 °С. The obtained organic gels are non-flammable polymers, and they can be used as thermal and fire retardant materials.

The effect of bifunctional catalyst Pt/ZrO₂ on the yield and composition of products of abies wood and ethanol lignin hydrogenation in supercritical ethanol at temperature of 250 °C was established. In the process of abies wood hydrogenation, the catalyst Pt/ZrO₂ increases the degree of conversion of wood from 52.0 to 65.7 wt.%, the yield of liquid products from 31.0 to 38.1 wt.%,.%, and also increases the content of monomeric compounds in the liquid products. In the presence of catalyst, the cellulose content in the solid product of wood catalytic hydrogenation reaches to 77.1 wt.%, and the content of lignin and hemicelluloses decreases to 21.2 wt.% and 1.7 wt.%, respectively. In the process of ethanol lignin hydrogenation the catalyst Pt/ZrO₂ increases the degree of lignin conversion from 86.0 to 99.4 wt.%, the yield of liquid products from 75.0 to 90.0 wt.%, and also reduces the yield of solid residue from 14.0 to 0.6 wt.% and the yield of gases from 4.7 to 3.3 wt.%. Thus, the polysaccharides of wood biomass complicate the reductive depolymerization of native lignin in comparison with the depolymerization of isolated ethanol lignin. The use of the catalyst Pt/ZrO₂ makes it possible to fractionate the abies wood in supercritical ethanol at 250 °C on solid product with a high content of cellulose, as well as liquid and gaseous products from lignin and hemicelluloses

The work describes a one-stage method of cellulose obtaining from fir wood based on peroxide delignification of wood under mild conditions (100 °C, atmospheric pressure) in the presence of acetic acid, water and catalyst of 2% wt. H2SO4. The possibility of obtaining cellulose with a residual lignin content

This article focuses on the aqueous complexation between two flavonoids (morin and morinsulfonate) and Pb2+ at constant ionic strength I=0.5 M (NaClO4). The determination of stability constants of ML complexes were performed at wide pH range. Two obtained constants are 14.8 ± 0.1 and 15.2 ± 0.1 logarithmic units for morin and morin-5’-sulfonic acid, respectively. For estimating the thermodynamic stability of the complexes studied, the Def2-SV(P)/DFT/PBE0/SMD method has been used. Different computational models were tested to describe the data obtained. The theoretical values of logK reproduce the experimental parameters within reasonable errors.

The acid–base properties, protonation activity, and complexing abilities of two substituted β-diketones have been studied. The equilibrium constants of dissociation (pKa) were obtained at constant ...

Sulfation of larch wood arabinogalactan (AG) with sulfamic acid in dimethylsulfoxide (DMSO) medium in the presence of urea was studied for the first time. The use of DMSO as a solvent instead of more toxic 1,4-dioxane allows to sulfate AG under homogeneous conditions. The sulfated AG with a high sulfur content (12.0-12.5 wt %) was produced by sulfation at a temperature of 85-90 °C, the molar ratio of AG / sulfating agent equal to 1:0.85 during 2-3 h. The introduction of sulfate groups into the structure of arabinogalactan was confirmed by the appearance of new absorption bands in FTIR and FT Raman spectra, characteristic for the vibrations of the sulfate groups. It was proved by 13C NMR spectroscopy that the predominant substitution of the primary hydroxyl groups at C6 carbon atoms of the terminal galactose units of main and side chains of arabinogalactan takes place. Simultaneously, the hydroxyl groups associated with C2 and C4 carbon atoms of galactose unit of the main chain are only partially sulfated. According to results of GPC study, the sulfated AG is characterized by a narrow molecular weight distribution with an average molecular weight of 18.8 kDa and a polydispersity of 1.3. Supplementary information The online version contains supplementary material available at 10.1007/s00226-021-01341-2.

fff; International audience; Catalytic hydrogenolysis in the medium of supercritical organic solvents is a promising way of wood lignins depolymerization into liquid products.In this study, for the first time, the catalytic properties of bifunctional catalysts Ru/C, Pt/ZrO2, NiCuMo/SiO2, containing nanosized metal particles on acidic groups are compared in the processes of aspen wood and ethanol lignin hydrogenolysis in supercritical ethanol.The most active catalysts are Ru/C and Pt/ZrO2 which provide the high conversion of wood (to 78.0 wt%), significant yield of liquid products (to 50.6 wt%) and low yield of solid rest (to 22.0 wt%) at temperature 250 °C and H2 pressure 9.0 MPa. These catalysts increase the yield of monomeric compounds in liquid products from 10.5 % to 50.4 % on mass of lignin.GC–MS analysis shows that alkyl derivatives of methoxyphenols (mainly propyl syringol and propyl guaiacol) are dominated in liquid products. Solid products of aspen wood catalytic hydrogenolysis contain mainly cellulose (to 82.2 wt%). Therefore, the catalytic hydrogenolysis in supercritical ethanol in the presence of by functional catalysts Ru/C and Pt/ZrO2 allows to fractionate the aspen wood biomass on cellulose and liquid products enriched with propyl syringol and propyl guaiacol.In catalytic hydrogenolysis of ethanol lignin the yield of alkyl derivatives of methoxyphenols is lower compared to wood. This is probably due to the reduced content of reactive β-O-4 bonds in the structure of ethanol lignin compared to native lignin of aspen wood. As follows from the results obtained, native lignin of wood is easier depolymerized to monomeric compounds in the process of catalytic hydrogenolysis than ethanol lignin, isolated from wood.According to GPC data, the catalysts shift to the region of lower molecular mass the molecular mass distribution of liquid products of aspen wood and ethanol lignin hydrogenolysis.

Supported gold and platinum particles on titanium oxide catalysts were evaluated in the oxidative depolymerization of lignins toward high added value aromatics under mild conditions (T: 150 °C, Pair: 20 bar, CNaOH: 10 g/L, 1 h). Kraft and ethanol Organosolv lignins were engaged in the study. Gold catalyst showed a strong tendency to further oxidize aromatics produced from lignin depolymerization to volatile compounds leading to very low yield in target molecules. On the contrary, platinum-based catalysts were allowed to observe enhanced yields that were attributed to its ability to preserve lignin’s substructure during the reaction. A kinetic model was constructed based on the results observed, which allowed us to identify the occurrence of condensation reactions during lignin oxidation and degradation of the produced aromatic compounds as the main limitations to reach high product yields. Insights on lignin oxidation and the catalyst’s role lead through this study would help to reach higher control over lignin valorization.

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.

SSCI-VIDE+CDFA+LDJ; International audience; Several lignin samples of varying botanical nature (softwood, hardwood, or annual plants) and extraction procedures (Kraft, Organosolv, or soda) were fully characterized by complementary techniques and engaged in “catalyst-free” depolymerization in air under basic conditions. Treatment of the complex reaction mixture was optimized to ensure reproducibility, careful analyses, and accurate data. After an optimization of the reaction conditions, we were able to recover high amounts of aromatic compounds (up to 19%wt). Additionally, we demonstrated a relation between lignin’s structure, i.e., the accessible phenol moieties and inter-unit linkages, and the yields of aromatic compounds, thus showing the importance of the extraction process to optimize lignin’s potential. This work provides valuable reference for developing further lignin depolymerization under basic media.

For the first time, the synthesis of water-soluble copper-containing microcrystalline cellulose sulfates (Сu-MCS) has been performed by the ion exchange method. The composition of the products has been studied by chemical methods and X-ray spectral microanalysis. The copper content in the Сu-MCS samples was 12.6–14.1%. The absence of sodium in the resulting polymer indicates the complete substitution of the sodium cations by the copper cations in the sodium salt of MCC sulfate. The structure of the copper-containing sulfates of microcrystalline cellulose has been confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and electron paramagnetic resonance (EPR). According to the XRD method, Сu-MCS and Na-MCS have an amorphous structure in contrast to the original MCC samples, which have a high degree of crystallinity. The EPR data have demonstrated the formation of a pseudocrystalline structure of the copper-containing salt system in the Сu-MCS samples. As shown by atomic-force microscopy, the surface of the Сu-MCS films consists of homogeneous crystallites, which have a spherical or slightly extended form with the size of about 70 nm. The film surface is quite homogeneous in its phase composition and contains no impurities.

The effect of the conditions of the acetylation process of raw and activated birch bark on the yield and composition of the products is investigated. The structure of biologically active betulin diacetate (BDA) is confirmed with physicochemical methods. The optimal regimes of the one-step original method for the production of BDA from raw and activated birch bark are established using the experimental and computational techniques.

The traditional method for obtaining microcrystalline cellulose (MCC) from wood raw material is multi-stage and it is based on the integration of environmentally hazardous processes of pulping and bleaching of cellulose and acid hydrolysis of amorphous part of cellulose. The paper describes an improved one-stage catalytic method of microcrystalline cellulose obtaining from softwood and hardwood based on peroxide delignification of wood in acetic acid-water medium under the mild conditions (100 °C, atmospheric pressure) in the presence of an environmentally safe solid catalyst TiO 2 . Experimental and mathematical optimization of the processes of MCC preparation by peroxide catalytic delignification of various types of wood was carried out. The following optimal modes of obtaining MCC with the yield 36.3–42.0 wt.% of abs. dry wood and residual lignin content ≤1.0 mas.%, hemicellulose ≤6.0 mas.% was established: for aspen – 5 wt.% H 2 O 2 , 25 wt.% CH 3 COOH, hydromodule = 10; for birch – 5 wt.% H 2 O 2 , 25 wt.% CH 3 COOH, hydromodule = 15; for abies – 6 wt.% H 2 O 2 , 30 wt.% CH 3 COOH, hydromodule = 15; for larch – 6 wt.% H 2 O 2 , 30 wt.% CH 3 COOH, hydromodule = 15.

Traditional processes of acid-catalyzed hydrolysis of wood are ineffective due to the low quality of formed glucose solutions contaminated with impurities that inhibit fermentation of glucose to ethanol. This problem grows during the hydrolysis of birch wood containing large amounts of hemicellulose. This work proposes producing quality glucose solutions using sulfuric acid (H2SO4, 80%) catalyzed hydrolysis at 25°C the cellulosic products formed during the catalytic peroxide delignification of birch wood. It is established that the composition of cellulosic products strongly affects the contents of glucose, xylose, and impurities inhibiting the enzymatic synthesis of bioethanol: furfural, 5-hydroxymethyl furfural, and levulinic acid. High yields (80.4–83.5 wt %) of glucose are achieved using cellulosic products produced by integrating the processes of sulfuric acid hydrolysis of hemicelluloses from birch wood and peroxide delignification of prehydrolyzed wood in the presence of catalysts: 2% H2SO4 and 1% TiO2. Concentration of inhibitors of enzymatic processes in these hydrolyzates is below the allowable limits. Hydrolyzates with maximum glucose content (86.4–88.5 wt %) and minimum concentration of inhibiting impurities produced by acid hydrolysis of cellulosic products treated with an 18% solution of NaOH. Gas chromatography, HPLC, and chromato-mass spectrometry are used to analyze the composition of hydrolyzates. Cellulosic products are examined by SEM, XRD, and chemical analysis.

For the first time, the fractionation of birch wood into microcrystalline cellulose, xylose and methoxyphenols is suggested based on the integration of alkali-acid pretreatments and hydrogenation in ethanol over a bifunctional Ru/C catalyst. It is established that removal of hemicelluloses during pretreatments of birch wood influences the yields of the liquid, gaseous and solid products of the non-catalytic and catalytic hydrogenation of pretreated samples in ethanol at 225 °C. The bifunctional Ru/carbon catalyst affects in different ways the conversion and yields of products of hydrogenation of the initial and acid- and alkali-pretreated birch wood. The most noticeable influence is characteristic of the hydrogenation of the acid-pretreated wood, where in contrast to the non-catalytic hydrogenation, the wood conversion and the yields of liquid products increase but the yields of the solid and gaseous products decrease. GC-MS, gel permeation chromatography and elemental analysis were used for characterization of the liquid product composition. The molecular mass distribution of the liquid products of hydrogenation of the initial and pretreated wood shifts towards the low-molecular range in the presence of the catalyst. From the GC-MS data, the contents of monomer compounds, predominantly 4-propylsyringol and 4-propanolsyringol, increase in the presence of the ruthenium catalyst. The solid products of catalytic hydrogenation of the pretreated wood contain up to 95 wt% of cellulose with the structure, similar to that of microcrystalline cellulose.

A new high-performance system for lactic acid (HL) extraction from glucose-containing solutions is proposed. Trialkylbenzylammonium sulfate (C7–C9 fraction) with p-tert-butyl phenol in a diluent is used as the extractant. The maximum extraction region for HL is found to be at pH = 5.0–7.0, which coincides with the range of optimal pH values for glucose conversion to lactic acid. In five extraction stages, at an organic to aqueous phase ratio of 1:1, the acid recovery is 96.7%. HL stripping is carried out with 2.0–3.0 M NaOH solutions, which achieves a significant increase in HL concentration. The stripping process in alkaline medium is easy (not less than 93.45% in one stage) due to the formation of trialkylbenzylammonium phenolate in the organic phase. Regeneration and conversion of the extractant to the SO4-form (TABAS) are carried out by treating the organic phase with sulfuric acid.

The structure of sodium salts of arabinogalactan (AG) sulfates obtained by sulfating AG of larch wood with a sulfamic acid–urea mixture in 1,4-dioxane was studied by the methods of Raman spectroscopy, X-ray diffraction (XRD) phase analysis, scanning electron microscopy (SEM), and atomic force microscopy (AFM). The introduction of sulfate groups into the structure of arabinogalactan was confirmed by the appearance in the Raman spectra of new absorption bands related to the deformation vibrations δ (SO3) at 420 cm–1 and δ (О=S=O) at 588 cm–1, stretching vibrations ν (C–O–S) at 822 cm–1, symmetrical stretching vibrations νs (O=S=O) at 1076 cm–1, and asymmetric stretching vibrations of νas (O=S=O) at 1269 cm–1. According to the XRD data, the amorphization of arabinogalactan structure occurs during the sulfation process. The SEM method revealed a significant difference in the morphology of the sulfated and starting arabinogalactan. The starting AG consists of particles of predominantly globular shape with a size of 10 to 90 μm; arabinogalactan sulfates, of particles of various shapes with sizes of 1–8 μm. According to the AFM, the surface of sulfated arabinogalactan film consists of rather homogeneous spherical particles about 70 nm in size. The root-mean-square value of the surface roughness is 33 nm. The surface of sulfated AG film does not contain impurities.

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.

The traditional processes of catalytic acid hydrolysis of wood are low effective due to the low quality of the formed glucose solutions contaminated with admixtures that inhibit fermentation of glucose to ethanol. This is a particularly acute problem in hydrolysis of birchwood containing hemicelluloses in large proportions. In the present paper, quality glucose solutions are suggested to produce via sulfuric acid hydrolysis (80 % H 2 SO 4 , 25 °C) of cellulose products formed during catalytic peroxide delignification of birchwood. The composition of the cellulose products are established to affect considerably the content of glucose, xylose and admixtures (furfural, 5-hydroxymethylfurfural, levulinic acid) in glucose, which inhibit enzymatic synthesis of bioethanol. High yields of glucose (80.4–83.5 wt %) are achieved with cellulose products prepared by integrated processes of sulfuric acid hydrolysis of birchwood hemicelluloses and peroxide delignification of pre-hydrolyzed wood in the presence of catalysts 2 % H 2 SO 4 and 1 % TiO 2 . Concentrations of inhibitors of enzymatic processes are lower of the admissible levels in these hydrolyzates. The hydrolyzates with the maximal glucose content (86.4–88.5 wt %) and minimal concentration of inhibiting impurities are prepared by acid hydrolysis of cellulose products treated with 18 % NaOH. The hydrolyzate composition was studied using gas chromatography, HELC, chromatomass spectroscopy. IRS, XPS and chemical techniques were used for characterization of cellulose products.

Composition and structure of microcrystalline cellulose (MCC) sulfates obtained by traditional and new advanced methods of MCC sulfation were compared. Data on the composition and structure of MCC sulfates synthesized in the medium of chlorosulfonic acid –1,4-dioxane and by sulfation of MCC with sulfamic acid in the presence of urea in N,N-dimethylformamide and diglyme were obtained with the use of elemental analysis, FTIR, Raman, 13C NMR, XRD, XPS, SEM and AFM methods. It was shown that MCC sulfates synthesized by new methods have more homogeneous composition and morphology as compared to sulfates obtained by known methods.

The new method of sulfated arabinogalactan modification by amino acids (glycine and ornithine) based on the ion exchange procedure was developed. The composition and structure of the reaction products obtained by interaction of sulfated arabinogalactan with amino acids were studied by elemental analysis and FTIR spectroscopy.

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.