• 임산에너지
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• 제17권1호
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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.

• 펄프종이기술
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• 제36권5호
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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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• 제45권6호
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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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• 제15권1호
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• pp.1-11
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• 1987

소나무 크라프트 펄프제조과정중 회수된 폐액으로 Black liquor-phenol formaldehyde. Methylolated kraft lignin-phenol formaldehyde 및 Lignin cake-phenol rein 세 종류의 접착제가 제조되었다. Black liquor-phenol formaldehyde resin 제조시 Phenol의 약 60%를 크라프트 폐액으로 대치할 수 있다. 본 접착제의 최적압착조건은 $160^{\circ}C$에서 7분간이였다.(상태접착력 : 15.77kg/$cm^2$ 내수접착력 : 8.54kg/$cm^2$). Methylolated kraft lignin-pheno] formaldehyde resin 제조시 Phenol의 약 80~90%를 Methylolated kraft lignin으로 대용할 수 있었다. 본 접착제 제조시 pH를 2.6 용매로서 Methanol, 접착제 1g 당 $0.2m\ell$ Formaldehyde를 첨가하는 것이 접착력이 가장 높았다(상대접착력 : 18.54kg/$cm^2$, 내수 접착력 : 10.08kg/$cm^2$. Lignin cake-phenol ressin에서 Phenol양과 Kraft lignin양이 1 : 1일 경우에 접착력이 높았다. 본 접착제의 최적 압착조건은 $150^{\circ}C$에서 4분간이었다.(상태 접착력 : 18.46kg/$cm^2$, 내수접착력 : 12.3kg/$cm^2$).

• 펄프종이기술
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• 제37권5호통권113호
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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.

• 펄프종이기술
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• 제31권2호
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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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• 제17권4호
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• pp.44-56
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• 1989

Kraft pulp 폐액에 다량 존재하는 lignin을 회수 이용하기 위하여 폐액을 조제하고 유기용매로 추출 정제하여 각 fraction별로 $^{13}C$-NMR 및 IR 스펙트라로 측정분석하였다. 그 결과 Kirk 방법보다는 M$\ddot{o}$rck 방법으로 정제한 시료가 lignin의 특징적인 signal들을 많이 나타나고 있는 점과 특히 MCS fraction은 방향핵이나 측쇄의 signal들이 잘 나타나고 있으며, KLI fraction에서는 methoxyl기와 C-${\beta}$의 signal이 잘 나타나고 있는 것을 알 수 있었다.

• 청정기술
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• 제27권2호
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• pp.190-197
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• 2021

펄프 및 제지산업에서 목재의 셀룰로오스 성분 활용 후 남는 부산물인 크라프트 리그닌(kraft lignin)은 촉매적 저분자화 공정을 통해 바이오연료나 고부가가치 페놀 단량체로 전환될 수 있다. 본 연구에서는 크라프트 리그닌의 효율적인 저분자화를 위한 촉매로 수소화 금속 및 산-염기점을 동시에 지니는 Ru-Mg-Al-oxide 복합 촉매를 제조하고, 리그닌 분해 성능을 평가하고자 하였다. 촉매 내 다양한 활성점들(산점, 염기점, 수소화 금속)이 리그닌 분해 반응에 미치는 영향을 파악하기 위해 MgO, Mg-Al-oxide, Ru-Mg-Al-oxide의 세 가지 촉매를 제조하여 초임계 에탄올 용매 상에서 리그닌 분해 반응을 수행하였고, 리그닌 분해 성능은 바이오오일(bio-oil) 수율 및 분자량, 그리고 페놀계 단량체 수율을 통해 평가하였다. 그 결과, Ru-Mg-Al-oxide 촉매가 다양한 활성점들의 시너지 효과로 인해 가장 높은 수율의 바이오오일 및 페놀 단량체들을 생산한다는 것을 확인하였다. Ru-Mg-Al-oxide 촉매 상에서 분해 효율을 최적화하기 위해 다양한 반응 조건(온도, 시간, 촉매양)에 따른 분해 효율을 평가하였고, 최종적으로 반응온도 350 ℃, 리그닌 대비 촉매 비율 10%, 4 h 반응을 통해 72%의 높은 바이오오일 수율과 무촉매 대비 3.5배 이상 증가한 페놀 단량체를 생산할 수 있었다.

• KSBB Journal
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• 제15권1호
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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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• 제60권4호
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• pp.499-505
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• 2022

본 연구에서는 크라프트 리그닌(Kraft Lignin)을 사용해 바닐린을 생산하는 공정의 개념 설계를 진행하였다. 기존 크라프트 리그닌은 대부분 저품질의 보일러 연료로 사용되거나 폐수로 버려지고 오직 2% 이하의 리그닌만 고품질의 제품으로 정제된다. 버려지는 크라프트 리그닌을 활용하기 위해 새로운 공정을 제안하였다. 기존 바닐린 생산 개념 공정은 NaOH를 사용한 알칼리 산화, 여과, 크로마토그래피, 결정화 단계로 진행됐다. 이중 상용화가 어려운 크로마토그래피를 용매 추출 공정으로 변경하였다. 제안된 용매 추출 공정의 바닐린 회수율 92.9%, 순도 99.5%이며, 이는 기존 크로마토그래피 공정과 유사한 수준이다. 크로마토그래피와 비슷한 결과를 보이는 용매 추출 공정이 기존 크로마토그래피 공정을 대체할 수 있는 이유를 분석하였다.