Abstract
Lignocellulosic biomass fractionation is typically performed using methods that are somehow harsh to the environment, such as in the case of kraft pulping. In recent years, the development of new sustainable and environmentally friendly alternatives has grown significantly. Among the developed systems, bio-based solvents emerge as promising alternatives for biomass processing. Therefore, in the present work, the bio-based and renewable chemicals, levulinic acid (LA) and formic acid (FA), were combined to fractionate lignocellulosic waste (i.e., maritime pine sawdust) and isolate lignin. Different parameters, such as LA:FA ratio, temperature, and extraction time, were optimized to boost the yield and purity of extracted lignin. The LA:FA ratio was found to be crucial regarding the superior lignin extraction from the waste biomass. Moreover, the increase in temperature and extraction time enhances the amount of extracted residue but compromises the lignin purity and reduces its molecular weight. The electron microscopy images revealed that biomass samples suffer significant structural and morphological changes, which further suggests the suitability of the newly developed bio-fractionation process. The same was concluded by the FTIR analysis, in which no remaining lignin was detected in the cellulose-rich fraction. Overall, the novel combination of bio-sourced FA and LA has shown to be a very promising system for lignin extraction with high purity from biomass waste, thus contributing to extend the opportunities of lignin manipulation and valorization into novel added-value biomaterials.
Highlights
Ethanol organosolv is referred to as a selective pre-treatment able to hydrolyze the internal bonds in lignins as well as lignin–hemicellulose bonds, contrary to the acidic hydrolysis conditions, which hydrolyses α-ether linkages, but it is likely that β-aryl ether bonds are broken under the conditions used in many organosolv-based processes [17]
The raw lignocellulosic material used in this work was pinewood sawdust and its lignin content was initially estimated to be 27.36 ± 7.93%, which is in agreement with the literature [1,34,35]
Two striking observations can be made from the analysis of Figure 1: (1) the increase in temperature favors the extraction yield; (2) the content of extracted lignin increases for longer extraction times
Summary
Lignocellulosic biomass valorization for potential use in the production of biochemicals, biofuels, biomaterials, and other added-value products, represents an important opportunity to reduce and valorize agroforest residues [1,2] In this respect, an important contribution can come from the pulping industry where considerable amounts of lignin-rich fractions are still poorly explored and valorized, despite their potential as a natural source of polyphenols [3]. Ethanol organosolv is referred to as a selective pre-treatment able to hydrolyze the internal bonds in lignins as well as lignin–hemicellulose bonds, contrary to the acidic hydrolysis conditions, which hydrolyses α-ether linkages (lignin), but it is likely that β-aryl ether bonds (cellulose) are broken under the conditions used in many organosolv-based processes [17] Another interesting system used in pulping is formic acid (FA), which is a by-product from lignocellulosic biomass processing [18]. The extracted lignin was further characterized by Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM)
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