• Journal of Korea Foresty Energy
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• v.18 no.1
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• pp.17-24
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• 1999

This study was conducted to examine the change in the structure of the lignin during liquefaction of kraft pulp lignin in Pinus korainsis and lignin sulfonic acid. The lignin liquefied compounds were extracted with chloroform from aqueous, liquefied lignins. Through the examination by IR, H($^{13}$C) - NMR and GC-MS spectrometers, phenolic compounds such as diguaiacol, acetic acid phenyl ester, phenol, 1-phenyl ethanone were identified with many of unknown phenolic compounds.

• KEPCO Journal on Electric Power and Energy
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• v.2 no.3
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• pp.447-452
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• 2016

It is imperative to develop an effective pathway to depolymerize lignin into liquid fuel that can be used as a bioheavy oil. Lignin can be converted into liquid products either by a solvent-free thermal cracking in the absence air, or thermo-chemical degradation in the presence of suitable solvents and chemicals. Here we show that the solvent-assisted liquefaction has produced promising results in the presence of metal-based catalysts. The supercritical ethanol is an efficient liquefaction solvent, which not only provides better solubility to lignin, but also scavenges the intermediate species. The concentrated sulfuric acid hydrolysis lignin (CSAHL) was completely liquefied in the presence of solid catalysts (Ni, Pd and Ru) with no char formation. The effective deoxy-liquefaction nature associated with scEtOH with aid hydrodeoxygenation catalysts, resulted in significant reduction in oxygen-to-carbon (O/C) molar ratio up to 61%. The decrease in oxygen content and increase in carbon and hydrogen contents increased the calorific value bio-oil, with higher heating value (HHV) of $34.6MJ{\cdot}Kg^{-1}$. The overall process is energetically efficient with 129.8% energy recovery (ER) and 70.8% energy efficiency (EE). The GC-TOF/MS analysis of bio-oil shows that the bio-oil mainly consists of monomeric species such as phenols, esters, furans, alcohols, and traces of aliphatic hydrocarbons. The bio-oil produced has better flow properties, low molecular weight, and high aromaticity.

• Journal of the Korean Wood Science and Technology
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• v.18 no.4
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• pp.79-85
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• 1990

Many kinds of acetosolv lignin including ricestraw and spruce lignin were pyrolyzed. and liquefied in the autoclave reactor using 50% tetralin and m-cresol solution respectively as soluble solvent and Co-Mo as catalyst. In order to promote deoxyhydrogenolysis reaction $H_2$ gas was supplied into the reactor. The ratio between lignin and the soluble solvent are lg and 10cc. The reaction conditions are $200^{\circ}-700^{\circ}C$ of reaction temperature, 10-50 atms of reaction pressure and 100-500rpm of the reactor stirrer. By the deoxyhydrogenolysis liquefaction reaction, the main chemical structures of lignin which are aryl-alkyl-${\beta}$-0-4 ether, phenylcoumaran and biphenyl etc. are easily destroyed into liqufied aromatic compounds and aliphatic compunds linked with aromatic compounds. The percent yield of monomeric phenols on the weight bvase of lignin reacted reached to 12-14% by the chemical analytic GC-MS etc.

• Journal of the Korean Wood Science and Technology
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• v.25 no.1
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• pp.1-7
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• 1997

Kraft oak lignin and ricestraw lignin from acetosolve pulping were dissolved in 50/50 mixture of tetralin/m-cresol solvent. The dissolved lignin was reacted in the pressurized autoclave which was operating at $350{\sim}500^{\circ}C$ of reaction temperature and 10~20 atms of reaction pressure respectively_Hydrogen pressure of 60~80kg/$cm^2$ was exercising into the pressurized autoclave reactor to create thermochemical hydrogenolysis reaction. It was identified by GLC, GC-MS and HPLC that the alkyl-aryl-${\beta}$-O-4 ether bond of lignin was cleaved and degraded into various smaller molecules of aromatic compound such as phenols and cresols under the reaction conditions around $300^{\circ}C$ and 10 atms of reaction temoerature and pressure. Hydrogenolysis reaction of lignin compound which was done above $500^{\circ}C$ of reaction temperature and 20 atms of reaction pressure showed that the amount of aromatic compound such as phenols and cresols degraded from reactant lignin was decreasing with newly present and increasing water out of product mixtures. It was supposed that new aliphatic compound of high molecular weight hydrocarbon is composed due to higher reaction temperature and pressure of hydrogenolysis reaction such as $500^{\circ}C$ and 20 atms, even though it was almost impossible, to identify what kind of degraded products it was by HPLC.

• Journal of the Korean Wood Science and Technology
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• v.23 no.2
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• pp.19-25
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• 1995

This research was carried out to investigate the methods of liquefaction with Pinus koraiensis, and chemical components of the liquefied wood by FT-IR analysis and pyrolysis-GC/MS. Acetylated wood powder was liquefied above 90% in phenol or m-cresol when treated at about 150$^{\circ}C$ for 30min., using some catalysts. Untreated wood powder was liquefied above 90% in phenol or m-cresol when treated at about 200$^{\circ}C$ for 60min., using some catalysts. The results of FTIR analysis, carbohydrates were terribly disintegrated, the other side lignin peaks were occurred in liquefied wood, particulary. The results of pyrolysis-GC/MS, the liquefied wood have clear four peaks, phenol, guaiacol, o-cresol and m-/p-cresol, due to degradation of lignin, particulary.

• Journal of the Korean Wood Science and Technology
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• v.32 no.1
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• pp.9-16
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• 2004

This research was carried out to investigate the component isolation method from liquefied waste paper. and isolated component was analyzed by molecular weight distribution with gel chromatography and nitrobenzene-oxidation analysis. In the aspect of liquefaction ratio, wet defibration fiber are better than dry defibration fiber because of wet defiberation fiber was easy to access of chemical solution. The optimal liquefaction condition of waste paper was treated at 190℃ for 60 min(cresol 2 ㎖, water 4 ㎖, phosphoric acid 0.5 ㎖ based on waste paper 1 g). In the liquefied waste paper, lignin and carbohydrate were separated with two interfacial layer(cresol layer, water layer). In the chemical analysis of isolated lignin, molecular weight distribution of isolated lignin was below 1,000.

• Solar Energy
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• v.18 no.3
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• pp.161-167
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• 1998

The effects of some additives(black liquor, wood and lignin) on the conversion of coal and product were investigated in the lab-scale, high pressure reacting system around $375^{\circ}C$. The addition of lignin to coal during liquefaction significantly increased the depolymerization of coal and enhanced the quality of the liquid products. Coprocessing of wood and coal at $400^{\circ}C$ increased yield of liquid product about 8%, but higher temperature above $400^{\circ}C$ reduced liquid product due to increase of gas products. The addition of black liquor resulted in an enhancement in coal conversion yields, however, the observed increase is lower than that obtained in the presence of NaOH because lignin present in black liquor is not very effective due to the $OH^-$ presence.

• 한국생물공학회:학술대회논문집
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• 2000.11a
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• pp.733-736
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• 2000

Lignin is usable as fuels and heavy oil additives if depolymerized to monomer unit, because the chemical structures are similar to high octane materials found in gasoline. In this study, the solvent-phase thermal cracking(solvolysis) of lignin was performed at the various temperature and time in a laboratory tubular reactor. Conversion yield was measured for the properties of thermal cracking and liquefaction reaction of lignin. Highest conversion yield when acetone was used as thermal cracking solvent was 55.5% at $350^{\circ}C$, 50minutes and highest tar generation were $260{\sim}350mg/g\;{\cdot}\;lignin$ at $250^{\circ}C$, and highest conversion yield after tar removal was 76.88% at $300^{\circ}C$, 30minutes. Conversion yield, product compositions and amounts were determined by tar degradation yield.

• Journal of the Korean Wood Science and Technology
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• v.19 no.4
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• pp.80-84
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• 1991

Lignocellulosic biomass including acetosolv ricestraw and spruce lignin were liquefied and converted into liquid hydrocarbons by catalytic hydroliquefaction reaction. These experimental works were carried out in 1-liter-capacity autoclave using 50% tetralin and m-cresol solution respectively as soluble solvent and Ni. Pd. Fe and red mud as catalyst. $H_2$ gas was supplied into the reactor for escaltion of deoxhydroenolysis reaction. Catalyst concentrations were 1 % of raw material based on weight. The ratio between raw materials and soluble solvent are 1g and 10cc. The reaction conditions are 400-$700^{\circ}C$ of reaction temperature, 10-50 atms of reaction pressure. The highest yield of hydrocarbon, so called "product oil" showed 32% and 5.5% of lowest char formation when red mud was used as catalyst. The product oil yields from those of other catalysts were in the range of 20-29%. The influence of different initial hydrogen pressures was examined in the range d 30-50 atms. A minimum pressure of 35 atms was necessary to obtain a complete recovery of souble solvent for recycling.