• 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.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 Korea Technical Association of The Pulp and Paper Industry
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• v.35 no.3
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• pp.74-78
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• 2003

The structural property of phenolic and non-phenolic lignin has an effect on the reaction rate of lignin by oxygen and chlorine dioxide respectively. Moreover, the undesirable degradation of cellulose followed by lignin degradation is influenced by chemical charge and reaction time. In this paper, several lignin model compounds were used to illuminate the interaction of oxygen and chlorine dioxide by varying the position of O and D(OD, DO, ODO and DOD), and gas chromatography method was used to investigate the degradation of lignin by determining the content of methoxyl groups in lignin. It was shown that structural properties of lignin models were more influential on the degradation and demethylation of lignin than the above combination. Combination of oxygen and chlorine dioxide, however, was more effective in degradation of lignin than only one stage, and three stages than two stages.

• Biotechnology and Bioprocess Engineering:BBE
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• v.9 no.4
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• pp.256-260
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• 2004

Melanin was decolorized by lignin peroxidase from Phanerochaete chrysosporium. This decolorization reaction showed a Michaelis-Mentens type relationship between the decolorization rate and concentration of two substrates: melanin and hydrogen peroxide. Kinetic constants of the decolorization reaction were 0.1 OD$\sub$475//min ($V_{max}$) and 99.7 mg/L ($K_{m}$) for melanin and 0.08 OD$\sub$475//min ($V_{max}$) and 504.9 ${\mu}$M ($K_{m}$) for hydrogen peroxide, respectively. Depletion of hydrogen peroxide interrupted the decolorization reaction, indicating the essential requirement of hydrogen peroxide. Pulsewise feeding of hydrogen peroxide continued the decolorizing reaction catalyzed by lignin peroxidase. These results indicate that enzymatic decolorization of melanin has applications in the development of new cosmetic whitening agents.

• Journal of the Korean Wood Science and Technology
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• v.47 no.4
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• pp.442-450
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• 2019

Despite its potential as a renewable source for fuels and chemicals, lignin valorization still faces technical challenges in many aspects. Overcoming such challenges associated with the chemical recalcitrance of lignin can provide many opportunities to innovate existing and emerging biorefineries. In this work, we leveraged a biomass genetic engineering technology to produce phenolic aldehyde-rich lignin structure via downregulation of cinnamyl alcohol dehydrogenase (CAD). The structurally altered lignin obtained from the Arabidopsis thaliana CAD mutant was pyrolyzed to understand the effect of structural alteration on thermal behavior of lignin. The pyrolysis was conducted at 400 and $500^{\circ}C$ using an analytical pyrolyzer connected with GC/MS and the products were systematically analyzed. The results indicate that aldehyde-rich lignin undergoes fragmentation reaction during pyrolysis forming a considerable amount of C6 units. Also, it was speculated that highly reactive phenolic aldehydes facilitate secondary repolymerization reaction as described by the lower yield of overall phenolic compounds compared to wild type (WT) lignin. Quantum mechanical calculation clearly shows the higher electrophilicity of transgenic lignin than that of WT, which could promote both fragmentation and recondensation reactions. This work provides mechanistic insights toward biomass genetic engineering and its application to the pyrolysis allowing to establish sustainable biorefinery in the future.

• Journal of the Korean Wood Science and Technology
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• v.43 no.3
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• pp.355-363
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• 2015

Asian lignin was efficiently depolymerized with supercritical ethanol and Ru/C catalyst at various reaction temperature (250, 300, and $350^{\circ}C$). Lignin-oil was subjected to several physicochemical analyses such as GC/MS, GPC, and elemental analysis. With increasing reaction temperature, the yield of lignin-oil decreased from 89.5 wt% to 32.1 wt%. The average molecular weight (Mw) and polydispersity index (Mw/Mn) of lignin-oil obtained from $350^{\circ}C$ (547Da, 1.49) dramatically decreased compare to those of original asian lignin (3698Da, 2.68). This is a clear evidence of lignin depolymerization. GC/MS analysis revealed that the yield of monomeric phenols involving guaiacol, 4-ethyl-phenol, 4-methylguaiacol, syringol, and 4-methysyringol increased with increasing reaction temperature, and these were mostly produced with applying hydrogen gas and Ru/C catalyst (76.1 mg/g of lignin). Meanwhile, the carbon content of lignin-oil increased whereas the oxygen content decreased with increasing reaction temperature, suggesting that hydrodeoxygenation was significantly enhanced at higher temperature.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.251.2-251.2
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• 2010

Plant biomass has been proposed to be an alternative source for petroleum-based chemical compounds. Especially, phenolic chemical compounds can be obtained from lignin by chemical depolymerization processes because lignin consists of complex aromatic polymer such as trans-p-coumaryl, coniferyl and sinapyl alcohols, etc. Phenolic chemical compounds from lignin were usually produced in super critical water. However, we applied Near-critical water (NCW) system because NCW is known as a good solvent for lignin depolymerization. Organic matter like lignin can be solved in NCW system and the system has a unique acid-base property without conventional non-eco-friendly chemicals such as sulfuric acid and sodium hydroxide. In this work, we tried to optimize the NCW depolymerization system by adjusting the processing variables such as reaction time, temperature and pressure. Moreover, the amount of additional phenol was optimized by changing the molar ratio between water and phenol. Phenol was used as capping agent to prevent re-polymerization of active fragment such as formaldehyde. Alkali-lignin was used as a starting material and characterized by a Solid State 13C-NMR, FT-IR and EA (Elemental Analysis). GC-MS analysis confirmed that o-cresol, p-cresol, anisole and 4-hydroxyphathalic acid were the main product and they were quantitatively analyzed by HPLC.

• Journal of Korea Foresty Energy
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• v.23 no.1
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• pp.45-68
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• 2004

The word of lignin is derived from the Latin word 'ligum' meaning wood. Lignin is complex polymer consisting of coniferyl alcohol, sinapyl alcohol and p-coumaryl alcohol unit and has an amorphous, three dimensional network structure which is hard to be hydrolyzed by acid. Lignin is found in the cell wall of plants lignified. The mode of polymerization of these alcohols in the cell wall lead to a heterogeneous branched and cross-linked polymer in which phenyl propane units are linked by carbon-carbon and carbon-oxygen bonds. This polymerization of precursors, p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol to lignin is formed by enzymic dehydrolyzation. The reaction is initiated by an electron transfer which results in the formation of resonance-stabilized phenoxy radical. The combination of these radicals produces a variety of dimers, trimers and oligomers and so on. Lignin research has been divided into basic and practical application field. The basic studies contains biosynthesis, chemical structure, distribution in the cell wall and reactivity by reductants, oxidants and organic solvents. The application research will be approached the reaction of lignin in various pulp making involving pulp bleaching and its effect on pulp qualities. Lignin also will be studied for the production of fine chemicals, polymer products and the conservation into an energy source like petroleum oil because the amount of lignin produced in pulp making process is more than 51,000,000 tons per year in the world. Both basic and application research must lay emphasis on the development for the utilization of lignin and the pulping process. But these researches can not be completed without understanding lignin structure containing functional groups. Therefore, this paper was focused on the review of lignin formulation which has been studied since 1948 in chronological order. This review was based on monomers, dimers, trimers and tetramers of phenyl propane unit structures which were isolated and identified by different methods from various wood.ious wood.

• 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.

• Journal of Environmental Health Sciences
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• v.23 no.2
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• pp.35-43
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• 1997

A study on the effect of the biodegradability of the composting bulking agent in the swine manurecomposting was carried out in a batch system. The purpose of this study is to prove the effect of the biodegradability of the composting-bulking agent on the efficiency of the composting. In this study, it is the lignins: Klason-Lignin in the volatile solid that the index of the biodegradability of the composting-material mixes which are pig manure-rice straw pig manure-sawdusts pig manuremixture of rice and ricestraw (2:1) pig manure-mixture of rice and sawdust (1:1). It was carried out in the same condition (moisture contents, air supply rate, C/N ratio, initial input weight, porosity-structure) except the biodegradability of the raw material mixes. One of the results from this study is that the biodegradability of the bulking agent in the sense of the VS lignin content is not an insignificant factor in composting reaction. The less contents of the lignin in VS, the more efficiencies of the cornposting reaction in use of these parameters for the degree of the reaction: temperature, the trends of the ash contents, the change pattern of the C/N ratio. Under some assumptions, it is able to induce rough model on the relation of the VS lignin contents with the efficiency of the degradability. In this model, the biodegradability of the bulking agent is not an insignificant factor however, it is flexible within some degrees of range.