• 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.

• Journal of Korea Technical Association of The Pulp and Paper Industry
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• v.36 no.5 s.108
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• pp.62-68
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• 2004

The amount of non-lignin components in unbleached and oxygen-delignified kraft pulps and their impact on lignin determinations was investigated. The lignin analyses investigated were kappa number and Klason lignin in conjunction with acid-soluble lignin. The species investigated were loblolly pine, and aspen. The non-lignin components that impacted on lignin determination were residual extractives and hexenuronic acid in unbleached and oxygen-delignified kraft pulps. In the hardwoods, significant amounts of extractives remained after kraft pulping and oxygen delignification. These residual extractives in the hardwood pulps had an impact on the lignin determination, more so on the acid lignin method than kappa number. Hexenuronic acid only impacts on kappa number determination both softwood and hardwood pulps, not on acid lignin. Hexeneuronic acid contributed as lignin content more in aspen than pine pulps, and more in oxygen-delignified than unbleached kraft pulps. Impact of hexenuronic acid on should be corrected both softwood and hardwood pulps for accurate kappa number.

• Journal of the Korean Wood Science and Technology
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• v.45 no.6
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• pp.703-719
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• 2017

Miscanthus had a higher lignin content (19.5 wt%) and carbohydrate (67.6 wt%) than other herbaceous crops, resulting in higher pellet strength and positive effect on combustion. However, miscanthus also contains a high amount of hydrophobic waxes on its outer surface, cuticula, which limits the pellet quality. The glass transition of lignin and cuticula were related to forming inter-particle bonding, which determined mechanical properties of pellet. To determine the effects of surface waxes, both on the pelletizing process and the pellet strength were compared with raw and extracted samples through solvent extraction. In addition, to clarify the relationship between pellet process parameters and bonding mechanisms, the particle size and temperature are varied while maintaining the moisture content of the materials and the die pressure at constant values. Furthermore, kraft lignin was employed to determine the effect of kraft lignin as an additive in the pellets. As results, the removal of cuticula through ethanol extractions improved the mechanical properties of the pellet by the formation of strong inter-particle interactions. Interestingly, the presence of lignin in miscanthus improves its mechanical properties and decreases friction against the inner die at temperatures above the glass transition temperature ($T_g$) of lignin. Consequently, it could found that the use of kraft lignin as an additive in pellet reduced friction in the inner die upon reaching its glass transition temperature.

• Journal of the Korean Wood Science and Technology
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• v.15 no.1
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• pp.1-11
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• 1987

A kraft black liquor obtained from pulping of pine (Pinus densiflora Sieb et Zucc) was used for producing three kinds of adhesive such as black liquor-phenol formaldehyde resin, methyloeated kraft lignin-phenol formaldehyde resin, and lignin cake-phenol resin. In case of producing black liquor-phenol formaldehyde resin, about 60 percent of the phenolic resin could be replaced by black liquor. Also the optimal press condition appeared to be $160^{\circ}C$ for 7 min. (l5.77Kg/$cm^2$ in dry test, 8.54Kg/$cm^2$ in 4 hr. boil test). Phenol could be substituted up to 80-90 percent by methylolated kraft lignin. The suitable conditions of factors affecting bond quality were pH to 2.6, methanol as solvent and 0.2ml formaldehyde per 1g of the adhesives, respectively. The optimal press condition was $150^{\circ}C$ for 4 min. (188.54Kg/$cm^2$ in dry test, 10.08Kg/$cm^2$ in 4 hr. boil test). In preparing lignin cake-phenol resin, a suitable mixing ratio of phenol to powered kraft lignin was one to one by weight. The optimal press condition was $150^{\circ}C$ for 4 min.(18.46Kg/$cm^2$ in dry test, 12.31Kg/$cm^2$ in 4 hr. hoil test).

• Journal of Korea Technical Association of The Pulp and Paper Industry
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• v.37 no.5 s.113
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• pp.50-55
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• 2005

In previous report, we investigated the impact of hexeneuronic acid and some residual extractiveson lignin determination. These non-lignin components severely interfered lignin content determination which also affect on the oxygen delignification comparison between aspen and pine unbleached kraft pulps. Very different pattern was observed whether based on uncorrected conventional kappa number or based on corrected kappa number in oxygen delignification comparison. Lower kappa number aspen pulps showed poor response to oxygen delignification when kappa number was used as lignin determination method but better response with using the acid lignin method. Phenolic hydroxyl group in kraft pulps were also compared based on uncorrected or corrected kappa numberfor lignin content. Based on uncorrected kappa number, lower kappa number oxygen-delignified pulps had lower phenolic hydroxyl group. However, lower kappa number oxygen-delignified pulps showed much higher phenolic hydroxyl group based on the corrected lignin content. For accurate comparison for residual lignin properties from different pulps, lignin determination should be corrected from non-lignin components contribution to lignin.

• Journal of Korea Technical Association of The Pulp and Paper Industry
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• v.31 no.2
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• pp.8-14
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• 1999

A screening has been performed to find hyper-ligninolytic fungi, which degtrade beech and pine lignin extensively in order to broaden the understanding of the ligninolytic enzymes elaborated by various white-rot fungi. One hundred and twenty two ligninolytic strains were selected from decayed woods with a selective medium for screening ligninolytic wood-rotting fungi. Two of them, Phanerochaete sordida YK-624 and YK-472, showed much higher ligninolytic activity and selectivity in beech-wood degradation than typical lignin-degrading fungi, phanerochaete chrysosporium and Coriolus versicolor. They also degraded birch dioxane lignin and residual lignin in unbleached kraft pulp(UKP) much more extensively than P. chrysosporium and C. versicolor. During fungal treatment of beech wood-powder, the fungus strain P. sordida YK-624 showed higher activity of extracellular manganese peroxidase (MnP) in the medium than P. chrysosporium. It also showed MnP activity, which would not be lignin peroxidast during treatment of oxygen-bleached kraft pulp(OKP) and under enzyme-inducing conditin.

• Journal of the Korean Wood Science and Technology
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• v.17 no.4
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• pp.44-56
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• 1989

To recover much residual lignin from the black liquor of kraft pulp. the black liquor was extracted and purified with many organic solvents. Many kinds of lignins were isolated from each fraction obtained and the characteristics of these lignins investigated by $^{13}C$-NMR spectroscopy. If M$\ddot{o}$rck's method was compared with Kirk's method. M$\ddot{o}$rck's method was better than Kirk's method because the particular signals of each lignin occur more in the former than m the latter. Especially the $^{13}C$-NMR spectrum of the MCS fraction identifies with those of other researchers. The experiment that the kraft lignin from Pinus densiflora S. et Z. found in Korea was investigated by $^{13}C$-NMR spectroscopy was performed first in Korea.

• Clean Technology
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• v.27 no.2
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• pp.190-197
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• 2021

Kraft lignin is a by-product of the pulp and paper industry, obtained as a black liquor after the extraction of cellulose from wood through the Kraft pulping process. Right now, kraft lignin is utilized as a low-grade boiler fuel to provide heat and power but can be converted into high-calorific biofuels or high-value chemicals once the efficient catalytic depolymerization process is developed. In this work, the multi-functional catalyst of Ru-Mg-Al-oxide, which contains hydrogenation metals, acid, and base sites for the effective depolymerization of kraft lignin are prepared, and its lignin depolymerization efficiency is evaluated. In order to understand the role of different active sites in the lignin depolymerization, the three different catalysts of MgO, Mg-Al-oxide, and Ru-Mg-Al-oxide were synthesized, and their lignin depolymerization activity was compared in terms of the yield and the average molecular weight of bio-oil, as well as the yield of phenolic monomers contained in the bio-oil. Among the catalysts tested, the Ru-Mg-Al-oxide catalyst exhibited the highest yield of bio-oil and phenolic monomers due to the synergy between active sites. Furthermore, in order to maximize the extent of lignin depolymerization over the Ru-Mg-Al-oxide, the effects of reaction conditions (i.e., temperature, time, and catalyst loading amount) on the lignin depolymerization were investigated. Overall, the highest bio-oil yield of 72% and the 3.5 times higher yield of phenolic monomers than that without a catalyst were successfully achieved at 350 ℃ and 10% catalyst loading after 4 h reaction time.

• KSBB Journal
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• v.15 no.1
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• pp.22-26
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• 2000

Kraft Lignin which is produced abundantly in pulp industry, was chemically degraded into small oligomers and polymerized using horseradish peroxidase. Lignin acidolysis was optimized by controlling reaction time and HCI concentration. Acidolyzed lignin was polymerized and copolymers of acidolyzed lignin and phenol or p-cresol were synthesized. 70% of kraft lignin was degraded after acidolysis. Number average molecular weight of all lignin polymers were from 8,500 to 14,000 and did not show large difference. Differential scanning calorimeter analysis showed that acidolyzed lignin did not show any melting temparature under $300^{\circ}C$, which indicates that newly synthesized lignin polymers can be used in industry under mild condition.

• Korean Chemical Engineering Research
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• v.60 no.4
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• pp.499-505
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• 2022

This study presents a conceptual design of vanillin production from Kraft lignin. Most of the existing Kraft lignin is used as low-quality boiler fuel or discarded as wastewater, and only 2% or less of lignin has been refined into high-quality products. We propose the process developed in this study to utilize discarded Kraft lignin. The existing vanillin production concept process consisted of alkali oxidation using NaOH, filtration, chromatography, and crystallization. Chromatography, which is difficult to commercialize, was changed to a solvent extraction process. The recovery rate of vanillin of the proposed solvent extraction process is 92.9%, and the purity is 99.5%, which is similar to the existing chromatography process. The reason why the solvent extraction process showing similar results to chromatography can replace the existing chromatography process was analyzed.