• Journal of Korea Foresty Energy
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• v.20 no.1
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• pp.35-41
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• 2001

Lignin model compounds I-lV were pyrolyzed at 315$^{\circ}C$. The mixture compounds pyrolized were analyzed by GC-MS spectrometry. The results were summarized as follows : 1. From the pyrolysis of lignin model compound I and II, 0.45mo1 of guaiacol, 0.5mol of dimethoxyphenol(DMP), and 0.12 and 0.23mo1 of dimethoxyacetonphenone(DMAP) were produced respectively. 2. In the pyrolysis of lignin model compound III and IV, 0.26mol of guaiacol, 0.30mo1 of DMP, and 0.09 and 0.15mo1 of trimethoxyaretonphenone(TMAP) were produced respectively 3. Pyrolysis mechanism of lignin model compounds are dehydrated at first, and $\beta$-04 linkage cleavaged, and then guaiacol, DMP, DMAP and TMAP were produced. The above results show that lignin model compound I and II produce more aromatic compounds than lignin model compound III and IV. This is reason that veratryl unit structures may pyrolize easier than trimethoxyphenol unit structures. The closer research is proceeding.

• Journal of Korea Foresty Energy
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• v.17 no.1
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• pp.56-70
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• 1998

This study was carried out to investigate the structural characteristics of kraft lignin and the wood degrading characteristics, the productivity of ligninolytic enzymes and the enzymatic degradation of kraft lignin by white-rot fungi. To purify kraft lignin, precipitation of kraft pulping black liquors of pitch pine meal was done by titration with lN $H_{2}SO_{4}$ reaching to pH 2, and isolation of the precipitates done by centrifugation. The isolated precipitates from pitch pine were redissloved in lN NaOH, reprecipitated by titration with lN $H_{2}SO_{4}$, washed with deionized water, and kept ofr analysis after freeze drying. Fractionation of the precipitates in solution by successive extraction with $CH_{2}Cl_{2}$ and MeOH, and the fractionates were named SwKL, SwKL I, SwKL II, and SwKL III for pitch pine kraft lignin. The more molecular weights of kraft lignin increased, the less phenolic hydroxyl groups and the more aliphatic hydroxyl groups. Because as the molecular weights increased, the ratio of etherified guaiayl/syringyl(G/S ratio) and the percentage were increased. The spectra obtained by 13C NMR and FTIR assigned by comparing the chemical shifts of various signals with shifts of signals from autherized ones reported. The optimal growth temperature and pH of white-rot fungi in medium were $28^{\circ}C$ and 4.5-5.0, respectively. Especially, in temperature and pH range, and mycelial growth, the best white-rot fungus selected was Phanerochaete chrysosporium for biodegradation. For the degradation pathways, the ligninolytic fungus jcultivated with stationary culture using medium of 1% kraft lignin as a substrate for 3 weeks at $28^{\circ}C$. The weight loss of pitch pine kraft lignin was 15.8%. The degraded products extracted successively methoanol, 90% dioxane and diethyl ether. The ether solubles were analyzed by HPLC. Kraft lignin degradation was initiated in $\beta$-O-4 bonds of lignin by the laccase from Phanerochaete chrysosporium and the degraded compounds were produced from the cleavage of $C\alpha$-$C\beta$ linkages at the side chains by oxidation process. After $C\alpha$-$C\beta$ cleavage, $C\alpha$-Carbon was oxidized and changed into aldehyde and acidic compounds such as syringic acid, syringic aldehyde and vanilline. And the other compound as quinonemethide, coumarin, was analyzed. The structural characteristics of kraft lignin were composed of guaiacyl group substituted functional OHs, methoxyl, and carbonyl at C-3, -4, and -5 and these groups were combinated with $\alpha$ aryl ether, $\beta$ aryl ether and biphenyl. Kraft lignin degradation pathways by Phanerochaete chrysosporium were initially accomplished cleavage of $C\alpha$-$C\beta$ linkages and $C\alpha$ oxidation at the propyl side chains and finally cleavage of aromatic ring and oxidation of OHs.