António Velez Marques

Reactivity of syringyl and guaiacyl lignin units and delignification kinetics in the kraft pulping of Eucalyptus globulus wood using Py-GC-MS/FID

Eucalyptus globulus sapwood and heartwood showed no differences in lignin content (23.0% vs. 23.7%) and composition: syringyl-lignin (17.9% vs. 18.0%) and guaiacyl-lignin (4.8% vs. 5.2%). Delignification kinetics of S- and G-units in heartwood and sapwood was investigated by Py-GC-MS/FID at 130, 150 and 170°C and modeled as double first-order reactions. Reactivity differences between S and G-units were small during the main pulping phase and the higher reactivity of S over G units was better expressed in the later pulping stage. The residual lignin composition in pulps was different from wood or from samples in the initial delignification stages, with more G and H-units. S/G ratio ranged from 3 to 4.5 when pulp residual lignin was higher than 10%, decreasing rapidly to less than 1. The S/H was initially around 20 (until 15% residual lignin), decreasing to 4 when residual lignin was about 3%.

Variation of Lignin Monomeric Composition During Kraft Pulping of Eucalyptus globulus Heartwood and Sapwood

Abstract Heartwood and sapwood samples from Eucalyptus globulus were characterized by Py-GC/MS and GC-FID in respect to composition and content of lignin. The pyrolysis lignin-derived compounds were assembled by groups: “syringol,” “S-aldehydes,” “S-ketones,” “S-alcohols,” and “C11H12O3” (S-units); “guaiacol,” “eugenol,” “G-aldehydes,” “G-ketones,” “G-alcohols,” and “others” (G-units); “phenol” and “H-aldehydes” (H-units). Heartwood and sapwood had similar lignin content in an extractive-free basis (23.7% and 23.0%, respectively) and in lignin composition (S-units, 76.0% vs. 76.3%; G-units, 22.0% vs. 21.0%; H-units, 1.9% vs. 2.7%; S/G ratio 3.5 and 3.6). The wood samples were kraft pulped under isothermal conditions at 130°C, 150°C and 170°C and several cooking times. Heartwood and sapwood behaved similarly. At 130°C the delignification was slow with no significant selectivity in respect to lignin composition. At 150°C and 170°C the S-units were more susceptible to reaction and comparatively more removed, inducing a decrease of S/G ratio to 0.6. The main products to be extracted belong to “syringol” and “S-aldehydes,” while the residual lignin in pulps was enriched in “guaiacol,” “eugenol” (G-units), and “phenol” (H-units).

Ferulates and lignin structural composition in cork

Abstract The structure of lignin and suberin, and ferulic acid (FA) content in cork from Quercus suber L. were studied. Extractive-free cork (Cork), suberin, desuberized cork (Corksap), and milled-cork lignins (MCL) from Cork and Corksap were isolated. Suberin composition was determined by GC-MS/FID, whereas the polymers structure in Cork, Corksap, and MCL was studied by Py-TMAH and 2D-HSQC-NMR. Suberin contained 94.4% of aliphatics and 3.2% of phenolics, with 90% of ω-hydroxyacids and α,ω-diacids. FA represented 2.7% of the suberin monomers, overwhelmingly esterified to the cork matrix. Py-TMAH revealed significant FA amounts in all samples, with about 3% and 6% in cork and cork lignins, respectively. Py-TMAH and 2D-HSQC-NMR demonstrated that cork lignin is a G-lignin (>96% G units), with a structure dominated by β–O–4′ alkyl-aryl ether linkages (80% and 77% of all linkages in MCL and MCLsap, respectively), followed by phenylcoumarans (18% and 20% in MCL and MCLsap, respectively), and smaller amounts of resinols (ca. 2%) and dibenzodioxocins (1%). HSQC also revealed that cork lignin is heavily acylated (ca. 50%) exclusively at the side-chain γ-position. Ferulates possibly have an important function in the chemical assembly of cork cell walls with a cross-linking role between suberin, lignin and carbohydrates.