• Journal of the Korean Wood Science and Technology
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• 제52권2호
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• pp.101-117
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• 2024

The conversion characteristics of the major components of Liriodendron tulipifera were investigated during acid-catalyzed organosolv pretreatment. Glucan in L. tulipifera was slowly hydrolyzed, whereas xylan was rapidly hydrolyzed. Simultaneous hydrolysis and degradation of xylan and lignin occurred; however, after complete hydrolysis of xylan at higher temperatures, lignin remained and was not completely degraded or solubilized. These conversion characteristics influence the structural properties of glucan in L. tulipifera. Critical hydrolysis of the crystalline regions in glucan occurred along with rapid hydrolysis of the amorphous regions in xylan and lignin. Breakdown of internal lignin and xylan bonds, along with solubilization of lignin, causes destruction of the lignin-carbohydrate complex. Over a temperature of 160℃, the lignin that remained was coalesced, migrated, and re-deposited on the surface of pretreated solid residue, resulting in a drastic increase in the number and content of lignin droplets. From the results, the characteristic conversions of each constituent and the changes in the structural properties in L. tulipifera effectively improved enzymatic hydrolysis in the range of 140℃-150℃. Therefore, it can be concluded that significant changes in the biomass recalcitrance of L. tulipifera occurred during organosolv pretreatment.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 추계학술대회 논문집
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• pp.520-520
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• 2009

Organic by-products derived from cellulose and lignin during organosolv pretreatments of yellow poplar wood (Liriodendron tulipifera) in the presence of $H_2SO_4$ and NaOH as catalysts, respectively, were subjected to various analyses to elucidate their effects on further performance of biological ethanol fermentation and provide preliminary data for the structure and utilization of organosolv lignin. Monomeric sugars amounted to ca. 2.2-7.7% in the organosoluble fraction of the organosolv pretreatment with $H_2SO_4$, while significantly low amount of sugars (0.2-0.3%) were determined in that of the organosolv pretreatment with NaOH. In case of addition of $H_2SO_4$ during organosolv pretreatment of biomass, a fermentation of the organosoluble fraction could be considered as an essential process to increase an efficiency of biomass utilization as well as yield of bioethanol. Precipitates, insoluble by-products in the solvent mixture, were also cficiency oed by diverse analytical methods and revealed that these were typically composed of a lignin moiety regardless of catalyst. According to the results of nuclear magnetic resonance (NMR), Fourier Tcinsform Infrared Spectroscopy (FT-IR) and Gel permeation chromatograp r (GPC), the main components of precipitates seem to be lignin polymers. However, their structures could be slightly modified during pretreatment and mixed with some carbohydrates by chemical bonds and/or physical associations.

• 대한환경공학회지
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• 제39권10호
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• pp.568-574
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• 2017

본 연구는 폐목재로부터 organosolv 공정을 이용해서 리그닌을 분리할 때 영향을 미치는 주요 3개의 반응조건(반응시간($X_1$), 산 촉매의 농도($X_2$) 및 반응온도($X_3$))을 리그닌 회수율(y) 기준으로 최적화하였다. 중심합성계획법(central composite design, CCD)에 따라 반응온도 $136.4-203.6^{\circ}C$, 산촉매 농도 0-2.5%, 반응시간 26.36-93.64 분의 범위를 가진 실험계획을 수행해서 2차 모델식 및 최적조건을 수립하였다. 2차 모델식은 $y=-79.89+0.91X_1+9.8X_2-2.54{\times}10^{-3}X_1{^2}-2.11X_2{^2}$와 같이 얻었으며, 결정계수(coefficient of determination, $R^2$) 값은 0.8531으로 10% 이내의 유의수준에서 유의성을 나타냈다. 2차 모델식에 따라 예측되는 최고 리그닌 회수율은 12.46 g/100 g of dry wood이며 이때 최적 반응 조건은 반응온도 $178.2^{\circ}C$, 산 촉매 농도 2.32%으로 나타났다. 폐목재 대상 organosolv 공정에서의 리그닌 수율은 반응온도보다는 산 촉매 농도의 영향이 더 크게 나타났으며 반응시간에 의한 영향은 없는 것으로 나타났다. 모델의 변동성 분석(analysis of variance, ANOVA)에 따르면 리그닌 수율(y)에 대한 모델식의 유의확률은 p<0.001로 높은 유의성을 보였다. 최적조건에서 모델의 재현성을 검증한 결과 모델식이 실제공정을 적절하게 모사한 것으로 나타났다.

• 펄프종이기술
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• 제47권4호
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• pp.21-29
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• 2015

In this study, the feasibility of utilizing wood chips from pitch pine (Pinus rigida) was evaluated for bioethanol production by an organosolv pretreatment and enzymatic saccharification. When wood chips from pitch wood were pretreated with 75% (v/v) ethanol and 1.7% sulfuric acid as a catalyst at H-factor 2000, average pulp yield was 43.3%, which pretreated wood fibers showed higher glucan (55.8%) and lower lignin (12.2%) contents than untreated control (43.9% glucan and 27.8% lignin). After enzymatic saccharification, the organosolv pulps with 56.2% delignification rate reached above 97% conversion rate of cellulose to glucose. These results indicated that increasing the delignification rate causes micro pores on the surface of organosolv pulps resulting in improved the accessibility of enzyme onto the substrate. Moreover, it was in agreement with the SEM examination of wood fibers.

• Journal of the Korean Wood Science and Technology
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• 제41권1호
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• pp.19-32
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• 2013

본 연구에서는 백색부후균의 리그닌 분해 효소 시스템을 이용하여, 다양한 균주 중에서 목질계 바이오매스 유기용매 전처리 과정에서 발생한 리그닌(유기용매 리그닌)의 생분해에 적합한 우수 균주를 선별하고자 하였다. 우선 분양받은 15개의 백색부후균을 대상으로 shallow stationary cultur (SSC)배지와 malt extract broth (MEB)배지에 유기용매 리그닌의 첨가에 따른 Remazol Brilliant Blue R (RBBR)의 흡광도 변화를 측정하였다. RBBR 탈색능 결과, SSC 배지에서 Ceriporiopsis subvermispora, Ceriporia lacerate, Fomitopsis insularis, Phanerochaete chrysosporium, Polyporus brumalis, Stereum hirsutum 등 6종의 백색부후균에서 급격한 흡광도 변화를 나타냈다. 배양 초기에 급격한 흡광도 변화를 나타낸 6개의 백색부후균을 대상으로 균체 외 단백질 농도 및 리그닌 분해 효소 활성을 측정하였다. 선발된 6개의 균 중에서 S. hirsutum과 P. chrysosporium은 유기용매 리그닌을 첨가한 실험구에서 높은 단백질 농도가 측정되었다. 반면, 리그닌 분해 효소 활성은 F. insularis에서 배양 6일째에 manganese peroxidase (MnP) 활성이 1,545 U/mg, laccase 활성은 1,259 U/mg으로 최고 활성을 나타냈다. 결론적으로, 균체 외 단백질 농도 및 리그닌 분해 효소 활성이 전반적으로 높았던 $STH^*$와 MnP 및 laccase의 활성이 가장 높은 FOI가 유기용매 리그닌 생분해에 유리하게 작용할 것으로 판단된다.

• Membrane and Water Treatment
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• 제11권1호
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• pp.25-29
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• 2020

The purpose of this study was to investigate the characteristics of lignin fractionated from waste wood (WW) using a two-step process of ethanol organosolv pretreatment followed by ultrafiltration with membranes of different molecular weight cut-offs (1, 5 and 20 kDa). The different permeates obtained were characterized by fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA) and gel permeation chromatography (GPC). The analysis by FT-IR and NMR of these lignins showed that the lignin core was successfully separated from WW. TGA curves confirmed that the thermal properties of lignin fractionated by ultrafiltration were almost identical to each other. The results from GPC confirmed that fractionating of lignin was achieved by ultrafiltration. For the membrane fractionation process, values of molecular weight decreased as the cut-offs used to obtain the fractions became smaller. As a result, fractionating lignin by a two-step process allowed separating different fractions of lignin of different molecular weights yielded high purity without interference from existing pollutants in WW. The two-step process offers the possibility of using fractionated WW as an untapped source of lignin.

• Journal of the Korean Wood Science and Technology
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• 제38권2호
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• pp.149-158
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• 2010

Organosolv pretreatments which utilized sulfuric acid, sodium hydroxide and ammonia as catalysts were conducted to screen the effective catalyst for organosolv pretreatment of Liriodendron tulipifera. The enzymatic hydrolysis was achieved effectively with sulfuric acid (74.2%) and sodium hydroxide (63.7%). They were thus considered as effective catalysts for organosolv pretreatment of L. tulipifera. The organosolv pretreatments with sulfuric acid and sodium hydroxide showed a different behavior on the reaction mechanism. The pretreatment with sulfuric acid increased the biomass roughness and pore numbers. On the other hand, the pretreatment with sodium hydroxide enhanced the surface area due to the size reduction and minor defiberization which were caused by hemicellulose degradation at an initial stage and more defiberization by lignin degradation at a later stage. The organosolv pretreatment with sodium hydroxide was performed at several different conditions to evaluate effectiveness of sodium hydroxide as a catalyst for organosolv pretreatment. According to the results of enzymatic digestibility, the changes of chemical composition and the morphological analysis of pretreated biomass, it was suggested that the pretreatment time impacted primarily on enzymatic hydrolysis. Increase in surface area during the pretreatment was a major cause for improvement in enzymatic digestibility when sodium hydroxide was used as a catalyst.

• Journal of the Korean Wood Science and Technology
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• 제16권4호
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• pp.70-78
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• 1988

To separate and utilize the main components of hardwood (Quercus mongolica) by organosov pulping (ester pulping), chips were cooked at various conditions such as; the solvent ratio (acetic acid: ethylacetate: water, 50:25:25; 33:33:34; 25:50:25), maximum temperature (165, 170, $175^{\circ}C$), and cooking times (2, 2.5, 3 hr). The pulps were bleached by the sequences of CEDED, C/DEDED, PEDED. Lignin, sugars, and acetic acid were separated from black liquor and washing liquors. 1. The selective delignification at optimal pulp yield (43-45%) was obtained by cooking at acetic acid: ethylace tate: water ratio of 33:34:34 for 3 hr at $170^{\circ}C$. But in this case, kappa no. of the pulp was not reduced under 60 points. 2. Kappa no. of the pulp could be dropped by an acetone wash to remove reprecipitated lignin a t cooked pulp. 3. The unbleached pulps had a brightness of 45-50%, whereas the bleached pulps gave at 88-93% brightness. Tensile, burst, and tear strengths of the bleached pulps were lower than those of kraft pulp, especially in tear strength. The pulps which were bleached with CEDED sequence were higher in strengths than another bleaching sequences. 4. Lignin of 90-95%(lignin base on wood)was separated from black liquor and washing liquors, while the purified sugars and recovery of acetic acid were a low. An organic phase composed of acetic acid, ethylacetate, and water was separated to a two-phase system by proper adjustment of the solvent ratios.

• Journal of the Korean Wood Science and Technology
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• 제43권5호
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• pp.600-612
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• 2015

We investigated the optimization of the organosolv pretreatment of yellow poplar for bioethanol production. Response surface methodology was used to determine the optimal conditions of three independent variables (reaction temperature, reaction time, and sulfuric acid (SA) concentration). Reaction temperature is the most significant variable in the degradation of xylan and lignin in the presence of an acid catalyst, and ethanol production increased with a decrease in the lignin content. The highest ethanol concentration ($42.80g/{\ell}$) and theoretical ethanol yield (98.76%) were obtained at $152^{\circ}C$ (2.5 bar) with 1.6% SA for 16 min. However, because of excessive degradation of the raw material, the overall ethanol yield was less than under other pretreatment conditions which has approximately 50% of WIS recovery rate after pretreatment. The optimal conditions for the maximum overall ethanol yield ($146^{\circ}C$ with 1.22% SA for 15.9 min) were determined with a predicted yield of 17.11%, and the experimental values were very close (17.15%). Therefore, the quadratic model is reliable.

• Korean Chemical Engineering Research
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• 제59권1호
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• pp.54-59
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• 2021

섬유소계 바이오매스는 전분질계 바이오매스에 비해 리그닌이 많아 전처리가 필수적으로 요구된다. 섬유소계 바이오매스를 전처리하기 위한 용매인 에탄올은 효소당화(enzymatic hydrolysis)에 저해가 되는 물질을 분별하기 쉬우며, 증류를 과정을 통해 쉽게 재사용이 가능하다. 침출식 전처리 공정은 반응기 내에서 연속적으로 성분을 분별하여 고-액 분리가 용이하며 향후 스케일업에서도 유리하다. 본 연구에서는 이러한 장점들을 활용하여 대표 섬유소계 바이오매스인 옥수수대(corn stover)로 전처리를 진행하였으며 해당 공정을 밀대(wheat straw)와 거대억새(miscanthus)에 적용하여 추가적인 바이오매스의 적용 가능성을 확인하였다.