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Noble metal-based catalysts are widely used to intensify the processes of reductive fractionation of lignocellulose biomass. In the present investigation, we proposed for the first time using the inexpensive NiCuMo/SiO2 catalyst to replace Ru-, Pt-, and Pd-containing catalysts in the process of reductive fractionation of abies wood into bioliquids and cellulose products. The optimal conditions of abies wood hydrogenation were selected to provide the effective depolymerization of wood lignin (250 °C, 3 h, initial H2 pressure 4 MPa). The composition and structure of the liquid and solid products of wood hydrogenation were established. The NiCuMo/SiO2 catalyst increases the yield of bioliquids (from 36 to 42 wt%) and the content of alkyl derivatives of methoxyphenols, predominantly 4-propylguaiacol and 4-propanolguaiacol. A decrease in the molecular mass and polydispersity (from 1870 and 3.01 to 1370 Da and 2.66, respectively) of the liquid products and a threefold increase (from 9.7 to 36.8 wt%) in the contents of monomer and dimer phenol compounds were observed in the presence of the catalyst. The solid product of catalytic hydrogenation of abies wood contains up to 73.2 wt% of cellulose. The composition and structure of the solid product were established using IRS, XRD, elemental and chemical analysis. The data obtained show that the catalyst NiCuMo/SiO2 can successfully replace noble metal catalysts in the process of abies wood reductive fractionation into bioliquids and cellulose. [ABSTRACT FROM AUTHOR]

Noble metal-based catalysts are widely used to intensify the processes of reductive fractionation of lignocellulose biomass. In the present investigation, we proposed for the first time using the inexpensive NiCuMo/SiO2 catalyst to replace Ru-, Pt-, and Pd-containing catalysts in the process of reductive fractionation of abies wood into bioliquids and cellulose products. The optimal conditions of abies wood hydrogenation were selected to provide the effective depolymerization of wood lignin (250 °C, 3 h, initial H2 pressure 4 MPa). The composition and structure of the liquid and solid products of wood hydrogenation were established. The NiCuMo/SiO2 catalyst increases the yield of bioliquids (from 36 to 42 wt%) and the content of alkyl derivatives of methoxyphenols, predominantly 4-propylguaiacol and 4-propanolguaiacol. A decrease in the molecular mass and polydispersity (from 1870 and 3.01 to 1370 Da and 2.66, respectively) of the liquid products and a threefold increase (from 9.7 to 36.8 wt%) in the contents of monomer and dimer phenol compounds were observed in the presence of the catalyst. The solid product of catalytic hydrogenation of abies wood contains up to 73.2 wt% of cellulose. The composition and structure of the solid product were established using IRS, XRD, elemental and chemical analysis. The data obtained show that the catalyst NiCuMo/SiO2 can successfully replace noble metal catalysts in the process of abies wood reductive fractionation into bioliquids and cellulose.

An optimization of sulfation of abies ethanol lignin by complexes of sulfuric anhydride with pyridine and 1,4-dioxane has been performed. Conditions for the implementation of the sulfation of abies ethanol lignin by complexes of sulfur trioxide with 1,4-dioxane and pyridine that provide a high sulfur content (12.0–12.6%) have been experimentally found. It has been shown that a high sulfur content of 12.0–13.5% (mass) in the resulting ethanol lignin sulfate is achieved at a chlorosulfonic acid to ethanol lignin ratio of 20.22 : 1 mmol : g and a duration of the process of 60–120 min and does not depend on the origin of the sulfation complex. The structure and the composition of water-soluble sulfated ethanol lignin have been confirmed by FTIR spectroscopy, gel-permeation chromatography, and elemental analysis. The IR spectra of sulfated abies ethanol lignin, as compared with the IR spectra of initial ethanol lignin, have absorption bands in the regions of 1270–1260, 1220–1212, and 861–803 cm–1, which correspond to the vibrations of sulfate groups. Sulfated ethanol lignin from abies wood has a low degree of polydispersity as compared with initial lignin. In particular, an increase in Mw from ~1.5 to ~3.4 kDa in lignin sulfated for 30 min and a decrease in polydispersity from 2.59 to 1.22 in comparison with the initial ethanol lignin were observed. As the time of sulfation increased, the profile of the curve of the molecular weight distribution shifted toward the high-molecular-weight region with a simultaneous increase in polydispersity to 1.5 and in the mean molecular weight to ~4.3 kDa. [ABSTRACT FROM AUTHOR]

Abstract Wood densification can improve the strength of low density wood species and extend wood product applications. To enhance the wood compressive quality, chemical pretreatments for pristine wood have widely been used. Densified Abies wood was fabricated by combining NaOH/Na2SO3 solution treatment, hot-pressing and post mechanical fixation. The appearance, color, chemical composition, and physiology and mechanical properties before and after the densification treatment were examined by the colorimeter, FTIR and mechanical testing machine, respectively. Surface color of Abies wood was changed obviously after the densification. The values of brightness L* and b* decreased but the value of a* showed a slight increase in the densified wood. FTIR results confirmed that the color changes can be explained by the degradation of hemicellulose and lignin in wood cell walls and migration of extractives during the densification process. Sufficient removal of wood polymers resulted in the average compression ratio of about 80% in the radial direction of the natural wood. The density of densified wood increased with the wood thickness up to 1.227 g cm−1, accounting for a 169% increase compared to that of the pristine wood. Modulus of rupture (MOR) and modulus of elasticity (MOE) in the thickness direction of densified wood also markedly enhanced. Degradation of polymers in wood cell walls also was reconfirmed by the difference of fracture interface. All the results suggested that the densified softwood can be easily fabricated using the proposed method and the new densified softwood can be appropriately used as interior decoration materials.

Wood densification can improve the strength of low density wood species and extend wood product applications. To enhance the wood compressive quality, chemical pretreatments for pristine wood have widely been used. Densified Abies wood was fabricated by combining NaOH/Na2SO3 solution treatment, hot-pressing and post mechanical fixation. The appearance, color, chemical composition, and physiology and mechanical properties before and after the densification treatment were examined by the colorimeter, FTIR and mechanical testing machine, respectively. Surface color of Abies wood was changed obviously after the densification. The values of brightness L* and b* decreased but the value of a* showed a slight increase in the densified wood. FTIR results confirmed that the color changes can be explained by the degradation of hemicellulose and lignin in wood cell walls and migration of extractives during the densification process. Sufficient removal of wood polymers resulted in the average compression ratio of about 80% in the radial direction of the natural wood. The density of densified wood increased with the wood thickness up to 1.227 g cm−1, accounting for a 169% increase compared to that of the pristine wood. Modulus of rupture (MOR) and modulus of elasticity (MOE) in the thickness direction of densified wood also markedly enhanced. Degradation of polymers in wood cell walls also was reconfirmed by the difference of fracture interface. All the results suggested that the densified softwood can be easily fabricated using the proposed method and the new densified softwood can be appropriately used as interior decoration materials. [ABSTRACT FROM AUTHOR]

The kinetic study of abies wood delignification by HO in the medium acetic acid-water was first carried out in the presence of TiO catalyst under mild conditions: temperatures 70-100 °C, atmospheric pressure. The oxidative delignification process is described satisfactory by the first order equation in all temperature range. The rate constants varied between 0.80 and 12.3 × 10 min and the activation energy was near 81 ± 0.21 kJ mol. The optimal parameters of the delignification process, providing the effective fractionation of abies wood on microcrystalline cellulose and soluble lignin, were established by experimental and numerical methods. [ABSTRACT FROM AUTHOR]