ABSTRACT
A first systematic approach on the base catalyzed depolymerization (BCD) of five technical lignins derived from various botanical origins (herbaceous, hardwood and softwood) and covering the main three industrial pulping methods (soda, kraft and organosolv) is reported. This study provides a first of its kind in-depth quantification and structural characterization of two main BCD fractions namely lignin oil and lignin residue, describing the influence of the BCD process conditions. Depolymerization is evaluated in terms of lignin conversion, lignin oil yield, phenolic monomer selectivity and the production of lignin residue and char. Lignin oils were extensively characterized by size exclusion chromatography (SEC), GC-MS, GC-FID, 13C-NMR, HSQC NMR and elemental analysis. GC × GC-FID was used to identify and quantify distinct groups of monomeric compounds (methoxy phenols, phenols, dihydroxy-benzenes) in the lignin oil. The lignin oil yields (w/w) ranged from 20-31% with total monomer contents ranging from 48 to 57% w/w. SEC analysis indicated the presence of dimers/oligomers in the lignin oil, which through HSQC NMR analysis were confirmed to contain new, non-native interunit linkages. 13C NMR analyses of the lignin oils suggest the presence of diaryl type linkages (i.e. aryl-aryl, aryl C-O) evidencing deconstruction and recombination of lignin fragments during BCD. Irrespective of the lignin source, a residue, often regarded as 'unreacted' residual lignin was the main product of BCD (43 to 70% w/w). Our study highlights that this residue has different structural properties and should not be considered as unreacted lignin, but rather as an alkali soluble condensed aromatic material. HSQC, DEPT-135, 13C, and 31P NMR and SEC analyses confirm that the BCD residues are indeed more condensed, with increased phenolic hydroxyl content and lower molecular weights compared to all feed lignins. Subsequent BCD of solid residual fractions produced only low oil yields (6-9% w/w) with lower phenolic monomer yields (4% w/w) compared to original lignin, confirming the significantly more recalcitrant structure. Our study improves the overall understanding of the BCD process, highlights important feedstock-dependent outcomes and ultimately contributes to the complete valorization of BCD-derived lignin streams.
ABSTRACT
Fast pyrolysis bio-oil (FPBO), a second-generation liquid bioenergy carrier, is currently entering the market. FPBO is produced from biomass through the fast pyrolysis process and contains a large number of constituents, of which a significant part is still unknown. Various analytical methods have been systematically developed and validated for FPBO in the past; however, reliable methods for characterization of acetaldehyde, formaldehyde, and furfural are still lacking. In this work, different analysis methods with (HS-GC/ECD, HPLC, UV/Vis) and without derivatization (GC/MSD, HPLC) for the characterization of these components were evaluated. Five FPBO samples were used, covering a range of biomass materials (pine wood, miscanthus, and bark), storage conditions (freezer and room temperature), and after treatments (none, filtration, and vacuum evaporation). There was no difference among the methods for the acetaldehyde analysis. A significant difference among the methods for the determination of formaldehyde and furfural was observed. Thus, more data on the accuracy of the methods are required. The precision of all methods was below 10% with the exception of the HPLC analysis of acetaldehyde with an RSD of 14%. The concentration of acetaldehyde in the FPBO produced from the three different biomasses and stored in a freezer after production ranged from 0.24 to 0.60 wt %. Storage at room temperature and vacuum evaporation both decreased significantly the acetaldehyde concentration. Furfural concentrations ranged from 0.11 to 0.36 wt % for the five samples. Storage and after treatment affected the furfural concentration but to a lesser extent than for acetaldehyde. Storage at room temperature decreased formaldehyde similarly to acetaldehyde; however, after vacuum-evaporation the concentration of formaldehyde did not change. Thus, the analysis results indicated that in FPBO the equilibrium of formaldehyde and methylene glycol is almost completely on the methylene glycol side, as in aqueous solutions. All three methods employed here actually measure the sum of free formaldehyde and methylene glycol (FAMG).
