Technical lignin particles melt under relatively low temperature. This results in the problem in the continuous feeding and fluidization during lignin pyrolysis, which in turn limits its utilization on a large scale. In this study, two most available types of lignin have been used to investigate the lignin melting problem, which are Kraft lignin (KL) from pulping process and hydrolysis lignin (HL) from bio-ethanol production process. Elemental composition, thermal property and thermally decomposed derivatives of each sample are tested by elemental analyzer, TGA, DSC, and Py-GC/MS. Morphology, structure and crystal change before and after heat treatment are tested by microscopy, FTIR and XRD. All results suggest that lignin structure determines its melting properties. Kraft lignin from pulping process contains a less cross-linked structure. It melts under heating. On the other hand, hydrolysis lignin from hydrolysis process contains a highly crossed-linked and condensed structure. It does not melt before decomposition under heat treatment. Modifying lignin structure is suggested for the resolution of technical lignin melting problem.

This paper investigated the impact of the amounts of lignin and hemicelluloses on cellulose nanofibers (CNFs). Birch and spruce wood were used to prepare holocellulose and cellulose samples by classical methods. To better assess the effect of the chemical composition on the CNF performance and simplify the process for CNF preparation, no surface derivatization method was applied for CNF preparation. Increased amounts of hemicelluloses, especially mannans, improved the defibration process, the stability of the CNFs and the mechanical properties, whereas the residual lignin content had no significant effect on these factors. On the other hand, high lignin content turned spruce nanopapers yellowish and, together with hemicelluloses, reduced the strain-at-break values. Finally, when no surface derivatization was applied to holocellulose and cellulose samples before defibration, the controlled preservation of residual lignin and hemicelluloses on the CNFs indicate to be crucial for the process. This simplified method of CNF preparation presents great potential for forest-based industries as a way to use forestry waste (e.g., branches, stumps, and sawdust) to produce CNFs and, consequently, diversify the product range and reach new markets.

This paper presents the results of an accelerated aging test of biocomposites containing kraft lignin, where the resistance of the materials against humidity and light exposure was investigated. Low molecular weight lignin, modified with methacrylic anhydride (LWL-Met), was copolymerized with two commercial monomers: styrene (St) and methyl methacrylate (MMA). The biocomposites were obtained by a bulk polymerization method using alpha,alpha'-azoiso-bis-butyronitrile (AIBN) as a free radical polymerization initiator. The Shore D hardness of the obtained materials was determined before and after aging test. The changes in the chemical structures of polymers, as the result of aging were analyzed by using the attenuated total reflection Fourier transform infrared (ATR/FT-IR) spectroscopy method. The thermal behavior and stability of the obtained materials were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The surface topography was determined using the optical topography method to evaluate the changes on the surface of synthesized materials resulted from accelerated aging. Application of modified lignin as a biocomponent in the polymerization process and its influence on the properties of the obtained materials before and after the accelerated aging test are discussed.

This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating values, and thermal and adsorption properties of industrial hardwood and softwood kraft lignins. The aim of the research was to develop a simple approach for obtaining lignin fractions with tailored properties for applications in certain materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations, were found to be efficient for separating spruce and eucalyptus kraft lignins into fractions with low polydispersities. The ethanol fraction of spruce and the ethyl acetate fraction of eucalyptus afforded the highest yields. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material was characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and P-31 NMR spectro-scopy. The thermal properties of the lignin samples were studied using thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) was obtained through the direct measurement of weight changes in each experimental curve, and the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The adsorption properties of fractionated kraft lignins were studied using methylene blue dye. The correlations observed between molecular weight, composition and functionality and the thermal, radical scavenging and adsorption properties of the lignin fractions provides useful information for selecting the appropriate solvent combinations for specific applications of lignin raw materials (including their use as antioxidants, biofuels or sorbents in water treatment processes).

Lignin fractions having different molecular weights and varied chemical structures isolated from kraft lignins of both softwood and hardwood via a sequential solvent fractionation technique were incorporated into a tunicate cellulose nanofibers (CNF)-starch mixture to prepare 100% bio-based composite films. The aim was to investigate the impact of lignin structural diversity on film performance. It was confirmed that lignin's distribution in the films was dependent on the polarity of solvents used for fractionation (acetone > methanol > ethanol > ethyl acetate) and influenced the optical properties of the films. The -OH group content and molecular weight of lignin were positively related to film density. In general, the addition of lignin fractions led to decrease in thermal stability and increase in Young's modulus of the composite films. The modulus of the films was found to decrease as the molecular weight of lignin increased, and a higher amount of carboxyl and phenolic -OH groups in the lignin fraction resulted in films with higher stiffness. The thermal analysis showed higher char content formation for lignin-containing films in a nitrogen atmosphere with increased molecular weight. In an oxygen atmosphere, the phenol content, saturated side chains and short chain structures of lignin had impacts on the maximum decomposition temperature of the films, confirming the relationship between the chemical structure of lignin and thermo-oxidative stability of the corresponding film. This study addresses the importance of lignin diversities on composite film performance, which could be helpful for tailoring lignin's applications in bio-based materials based on their specific characteristics.

Lignin, a major component of lignocellulosic biomass, is generated in enormous amounts during the pulp production. It is also a major coproduct of second generation biofuels. The effective utilization of lignin is critical for the accelerated development of the advanced cellulosic biorefinery. Low cost and availability of lignin make it attractive precursor for preparation of a range of carbon materials, including activated carbons, activated carbon fibers (CF), structural CF, graphitic carbons or carbon black that could be used for environmental protection, as catalysts, in energy storage applications or as reinforcing components in advanced composite materials. Technical lignins are very diverse in terms of their molecular weight, structure, chemical reactivity, and chemical composition, which is a consequence of the different origin of the lignin and the various methods of lignin isolation. The inherent heterogeneity of lignin is the main obstacle to the preparation of high-performance CF. Although lignin-based CF still do not compete with polyacrylonitrile-derived CF in mechanical properties, they nevertheless provide new markets through high availability and low production costs. Alternatively, technical lignin could be used for production of carbon adsorbents, which have very high surface areas and pore volumes comparable to the best commercial activated carbons. These porous carbons are useful for purifying gas and aqueous media from organic pollutants or adsorption of heavy metal ions from aqueous solutions. They also could be used as catalysts or electrodes in electrochemical applications.

Lignin, which is the second most abundant biomass component and has carbon-rich phenolic content, is a promising renewable raw material for multiple applications, such as carbon fibers, adhesives, and emulsifiers. To use lignin efficiently, it is important to ensure its purity and homogeneity. As a result, the separation of lignin into fractions with high purity and narrow molecular-weight distributions is likely a prerequisite for several applications. Ultrafiltration using ceramic membranes has many advantages, including enabling direct lignin extraction from Kraft pulp cooking liquors without pH and temperature adjustment. One challenge with membrane filtration using such a system is the potential for reduced membrane performance over time, which is associated with fouling. In this study, LignoBoost Kraft lignin was fractionated using a ceramic membrane with a molecular weight cut-off of 1 kDa. The separation behavior during ultrafiltration fractionation was investigated and the antioxidant properties of the recovered low-molecular-weight (low-MW) lignin samples were evaluated. Using this model system, the permeate fluxes were unstable during the 100 h of membrane operation. However, a decrease in the average MW in the permeate over time was observed. The shift in MW was most pronounced for virgin membranes, while a more stable MW distribution was evident for membranes subjected to multiple cleaning cycles. According to 2D NMR analysis, low-MW lignin that was recovered after 100 h of operation, consisted of smaller lignin fragments, such as dimers and oligomers, with a high content of methoxy-groups. This was confirmed using the size exclusion chromatography method, which indicated an weigh average molecular weight in the range of 450–500 Da. 31P NMR spectroscopy showed that, despite the lower total content of phenolic OH groups, the low-MW sample had a higher proportion of non-condensed phenolic OH groups. The results of the antioxidant tests demonstrated the strong potential of lignin and its low-MW fraction as a natural antioxidant, particularly for lipid-containing systems. The low-MW lignin fraction showed better antioxidant activity than the non-fractionated LignoBoost lignin in the kinetic oxygen radical absorbance capacity (ORAC) test and demonstrated three-fold stronger inhibition of the substrate (fluorescein) than the reference antioxidant Trolox (a water-soluble derivative of vitamin E).

New hybrid sorbents were synthesized from technical lignins and silica and were applied for the removal of Methylene Blue dye (MB) from aqueous solution. Kraft softwood lignins from LignoBoost (LBL) and CleanFlowBlack (CFBL) processes were used to understand the influence of molecular weight and functionality of initial lignins on the properties of the final hybrids. The synthesized materials were applied as adsorbents for the removal of MB from aqueous solutions. The effects of parameters such as contact time, initial concentration of dye and initial pH on the adsorption capacity were evaluated. The hybrids exhibited higher adsorption capacity than the initial macromolecules of lignin with respect to MB. The hybrid based on CFBL exhibited an adsorption capacity of 60 mg/g; this value was 30% higher than the capacity of the hybrid based on LBL, which was 41.6 mg/g. Lignin hybrid materials extract 80-99% of the dye in a pH range from 3 to 10. The equilibrium and kinetic characteristics of MB uptake by the hybrids followed the Langmuir isotherm model and pseudosecond-order model, rather than the Freundlich and Temkin models, the pseudo-first-order or the intraparticle diffusion model. The attachment of the dye to the hybrid surface was confirmed via FE-SEM and FTIR spectroscopy. The mechanism for MB adsorption was proposed. Due to the high values of regeneration efficiency of the surface of both lignin-silica hybrid materials in 0.1 M HCl (up to 75%) and ethanol (99%), they could be applied as effective sorbents in industrial wastewater treatment processes.

The development of advanced hybrid materials based on polymers from biorenewable sources and mineral nanoparticles is currently of high importance. In this paper, we applied softwood kraft lignins for the synthesis of lignin/SiO₂ nanostructured composites. We described the peculiarities of composites formation in the sol-gel process through the incorporation of the lignin into a silica network during the hydrolysis of tetraethoxysilane (TEOS). The initial activation of lignins was achieved by means of a Mannich reaction with 3-aminopropyltriethoxysilane (APTES). In the study, we present a detailed investigation of the physicochemical characteristics of initial kraft lignins and modified lignins on each step of the synthesis. Thus, 2D-NMR, ³¹P-NMR, size-exclusion chromatography (SEC) and dynamic light scattering (DLS) were applied to analyze the characteristics of pristine lignins and lignins in dioxan:water solutions. X-Ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) were used to confirm the formation of the lignin–silica network and characterize the surface and bulk structures of the obtained hybrids. Termogravimetric analysis (TGA) in nitrogen and air atmosphere were applied to a detailed investigation of the thermal properties of pristine lignins and lignins on each step of modification. SEM confirmed the nanostructure of the obtained composites. As was demonstrated, the activation of lignin is crucial for the sol-gel formation of a silica network in order to create novel hybrid materials from lignins and alkoxysilanes (e.g., TEOS). It was concluded that the structure of the lignin had an impact on its reactivity during the activation reaction, and consequently affected the properties of the final hybrid materials.

Currently, it is necessary to develop new methods and materials for solving the problem of environmental pollution by various toxicants. For these purposes, vegetal materials can be used. In this study, efficient low-cost sorbents based on walnut shells, an agro-industrial by-product, were prepared by treatment with acetic acid or a mixture of acetic acid and hydrogen peroxide. It was shown that the treatments significantly affected the composition and structure of walnut shells and their sorption properties with respect to organic dyes (methylene blue, methyl violet, and murexide) and heavy metal ions. Methylene blue dye was used for additional studies on the effect of pH, contact time and kinetics of sorption. The maximum adsorption rate of the dye occurred within the first 30 min of contact, during which the concentration of methylene blue in the solution was reduced by more than half. Full sorption equilibrium was reached within 180-230 min for studied samples. The adsorption kinetics of methylene blue was found to best be described by pseudo-second-order kinetic model. It was shown that dyes adsorption processes were well described by Freundlich model, which takes into consideration the heterogeneity of the surface of the adsorbent. The obtained plant sorbents are characterized by a high sorption capacity for heavy metal ions (18-29 mg/g for Fe3+ and 33-44 mg/g for Cu-2). Due to their numerous advantages, such as the high sorption capacity, high availability and low cost of raw materials, simplicity of disposal and nontoxicity, the obtained natural sorbents may have a wide practical use in industrial wastewater treatment. [GRAPHICS] .