Characterization Of Dissolved Lignins From Acetic Acid Lignofibre (Lgf) Organosolv Pulping And Discussion Of Its Delignification Mechanisms
HOLZFORSCHUNG(2015)
摘要
Birch chips were cooked by means of the Lignofibre (LGF) organosolv process in acetic acid (AA) and phosphinic acid (H3PO2) at 150 degrees C. The delignification rate and structure of the dissolved lignin was followed as a function of time. The degree of delignification increased steadily up to 88% during the 120 min treatment time. The dissolved lignins were precipitated from the spent liquor (SL) by water addition, washed, and purified for the analyses. Elemental analysis, P-31 nuclear magnetic resonance (NMR), heteronuclear single-quantum coherence (HSQC) NMR, pyrolysis-gas chromatography/mass spectrometry (GC/MS), and gel permeation chromatography (GPC) were applied for the structural elucidation. It was found that the cleavage of the beta-aryl ether linkages is the main reaction leading to delignification, accompanied by the formation of free phenolic hydroxyl groups and reduction in the content of aliphatic hydroxyl groups. The structure of the dissolved lignin remained the same after the drastic changes at the early stages of cooking (up to 30 min cooking time), indicating that secondary reactions (e.g., condensation) do not take place to a significant extent. H3PO2 probably enhances the acidolysis reaction via an ester derivative that both boosts the cleavage reaction and prevents the formation of the carbocation intermediate that induces condensation. Homolytic cleavage reactions may take place parallel to the acidolytic reactions.
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关键词
acetic acid, degradation mechanism, delignification, lignin, Lignofibre (LGF) process, organosolv pulping, phosphinic acid
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