Lignin is one of the wood and plant cell wall components that is available in large quantities in nature. Its polyphenolic chemical structure has been of interest for valorization and industrial application studies. Lignin can be obtained from wood by various delignification chemical processes, which give it a structure and specific properties that will depend on the plant species. Due to the versatility and chemical diversity of lignin, the chemical industry has focused on its use as a viable alternative of renewable raw material for the synthesis of new and sustainable biomaterials. However, its structure is complex and difficult to characterize, presenting some obstacles to be integrated into mixtures for the development of polymers, fibers, and other materials. The objective of this review is to present a background of the structure, biosynthesis, and the main mechanisms of lignin recovery from chemical processes (sulfite and kraft) and sulfur-free processes (organosolv) and describe the different forms of integration of this biopolymer in the synthesis of sustainable materials. Among these applications are phenolic adhesive resins, formaldehyde-free resins, epoxy resins, polyurethane foams, carbon fibers, hydrogels, and 3D printed composites.

Commercial forest plantations in Chile are dominated by pine (Pinus radiata) and eucalyptus (Eucalyptus globulus). Tree bark is the main by-product of the forestry industry and has low value, but great potential for use as an agricultural substrate. However, the direct use of bark fibers may cause plant phytotoxicity due to the presence of polyphenolic and other compounds. This study aims to evaluate the physicochemical properties of E. globulus and P. radiata bark after water extraction treatments. The phytotoxicity of the resulting extracted bark alone and that mixed with commercial substrates (coconut fiber, moss, peat, and composted pine) at different ratios (25 to 75 wt%) were assessed using the Munoo-Liisa vitality index (MLVI) test. For all treatments, the seed germination and growth of radish (Raphanus sativus) and Chinese cabbage (Brassica rapa) species were evaluated and compared to a commercial growing medium (peat) as a control. The optimal mixture for seed growth was determined to be 75% extracted E. globulus bark fiber and 25% commercial substrates such as peat (P), coconut fiber (C), moss (M), and composted pine (CP), as indicated by the MLVI and germination results. Two phytostimulant products, chitosan and alginate-encapsulated fulvic acid, were added to the best substrate mixture, with the purpose of improving their performance. Encapsulated fulvic acid at 0.1% w/v was effective in promoting plant growth, while chitosan at all of the concentrations studied was effective only for mixture 75E-25CP. The mixture of E. globulus fiber and commercial substrates, containing a high proportion of water-extracted fiber (75%), shows the potential to be used in the growth of horticultural crops and in the plant nursery industry.

The objective of this study was to investigate structural changes and lignin redistribution in Eucalyptus globulus pre-treated by steam explosion under different degrees of severity (S0), in order to evaluate their effect on cellulose accessibility by enzymatic hydrolysis. Approximately 87.7% to 98.5% of original glucans were retained in the pre-treated material. Glucose yields after the enzymatic hydrolysis of pre-treated material improved from 19.4% to 85.1% when S0 was increased from 8.53 to 10.42. One of the main reasons for the increase in glucose yield was the redistribution of lignin as micro-particles were deposited on the surface and interior of the fibre cell wall. This information was confirmed by laser scanning confocal fluorescence and FT-IR imaging; these microscopic techniques show changes in the physical and chemical characteristics of pre-treated fibres. In addition, the results allowed the construction of an explanatory model for microscale understanding of the enzymatic accessibility mechanism in the pre-treated lignocellulose.

Sulfomethylation of radiata pine kraft lignin was performed using formaldehyde and sodium sulfite under alkaline conditions to determine its potential as a mineral depressant for the separation of molybdenite and chalcopyrite by froth flotation. Optimal conditions for the sulfomethylation reaction were 20% (w/w) Na2SO3 at 130 °C for 4.2 h, which resulted in lignin with a sulfonate content of 2.2 mmol/g. Microflotation assays showed that the optimized sulfomethylated kraft lignin (OSKL) depressed the molybdenite in flotation by 93% using 200 mg/L OSKL, while only 5% chalcopyrite depression was achieved. The performance of OSKL was compared with those of commercial lignosulfonates, and the OSKL displayed a better ability to separate molybdenite and chalcopyrite, even at lower concentration doses. FTIR and 1H-NMR analyses showed that sulfonic groups were incorporated into the C5 position of the aromatic ring and into the aliphatic chain of the OSKL. The hydroxymethyl content of the OSKL was increased, and most β-O-4′, β-1′ and β-5′ bonds were broken, with the exception of the β-β’ bond. Sulfomethylation gives kraft lignin the chemical characteristics of a wood-based molybdenite depressant, making it an alternative to current reagents used in the chalcopyrite-molybdenite flotation process.

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Kraft pulp cellulose was hydrolyzed using sulfuric acid, under different thermophysical conditions of temperature, time, pulp concentration, and sonication time. The experimental design revealed the effect of these conditions and their interaction on the hydrolysis yield obtained. In addition, the top five cellulose nanocrystals (CNCs) yields from this experiment design were analyzed. The results obtained indicated that CNCs possess a morphology that can be described as individualized rod particles, with average diameters less than 50 nm and different size distribution. In the analysis of CNCs features, significant Pearson correlations were established between the crystallinity of the CNC, CNC yield, and interplanar crystallites distance (Δd/d). The thermogravimetric (DTG) profiles exhibited two CNCs degradation stages, where the second stage CNCs degradation showed a significative correlation with CNC sulfur content. In our analysis, the crystallographic parameters exhibited a correlation with the mechanical behavior of the CNC, since the potential variation between the distances of the crystalline planes is related to the stress and deformation present in the crystallites of CNCs. This study provides new knowledge regarding CNCs, further enhancing information for CNC-based industries and the processability of CNCs for the development of new materials.

Eucalyptus globulus is the second most important economic forest species in Chile. Its main use is in the kraft pulp industry, where large amounts of bark waste are generated. Due to its fibrous characteristics, E. globulus bark is proposed as an alternative source of fibres for papermaking. This study focuses on obtaining fibres for liner paper manufacture. A neutral sulphite semi-chemical (NSSC) process was performed, varying the sodium sulphite (5% to 16%) and the sodium carbonate (2% and 4%) concentrations using two reaction temperatures (160°C and 170°C). The NSSC process at 170°C, 16% of sulphite, and 2% of sodium carbonate proved to be the best condition to obtain higher mechanical performance of papers. As the pulping conditions become more drastic, the yield drops, and the physicomechanical properties of paper increases. Results showed that pulps from E. globulus bark could turn into source of fibres for papermaking and other related products.

Cellulose nanocrystals (CNCs) are attractive materials due to their renewable nature, high surface-to-volume ratio, crystallinity, biodegradability, anisotropic performance, or available hydroxyl groups. However, their source and obtaining pathway determine their subsequent performance. This work evaluates cellulose nanocrystals (CNCs) obtained from four different eucalyptus species by acid hydrolysis, i.e., E. benthamii, E. globulus, E. smithii, and the hybrid En × Eg. During preparation, CNCs incorporated sulphate groups to their structures, which highlighted dissimilar reactivities, as given by the calculated sulphate index (0.21, 0.97, 0.73 and 0.85, respectively). Although the impact of the incorporation of sulphate groups on the crystalline structure was committed, changes in the hydrophilicity and water retention ability or thermal stability were observed. These effects were also corroborated by the apparent activation energy during thermal decomposition obtained through kinetic analysis. Low-sulphated CNCs (E. benthamii) involved hints of a more crystalline structure along with less water retention ability, higher thermal stability, and greater average apparent activation energy (233 kJ·mol−1) during decomposition. Conversely, the high-sulphated species (E. globulus) involved higher reactivity during preparation that endorsed a little greater water retention ability and lower thermal stability, with subsequently less average apparent activation energy (185 kJ·mol−1). The E. smithii (212 kJ·mol−1) and En × Eg (196 kJ·mol−1) showed an intermediate behavior according to their sulphate index.