Journal of the Korean Wood Science and Technology

The Korean Society of Wood Science & Technology (한국목재공학회)
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Degradation of Plant Lignin with The Supercritical Ethanol and Ru/C Catalyst Combination for Lignin-oil

초임계 에탄올과 루테늄 촉매에 의한 초본 리그닌의 오일화 반응

  • Park, Jeesu (Department of Forest Sciences, CALS, Seoul National University) ;
  • Kim, Jae-Young (Department of Forest Sciences, CALS, Seoul National University) ;
  • Choi, Joon Weon (Graduate School of International Agricultural Technology and Institute of Green-Bio Science and Technology)
  • 박지수 (서울대학교 농업생명과학대학 산림과학부) ;
  • 김재영 (서울대학교 농업생명과학대학 산림과학부) ;
  • 최준원 (서울대학교 국제농업기술대학원/그린바이오연구원)
  • Received : 2014.10.28
  • Accepted : 2014.12.10
  • Published : 2015.05.25
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Abstract

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.

본 연구에서는 초임계 에탄올 및 Ru/C 촉매를 이용하여 초본류 바이오매스 유래 아시안 리그닌을 효과적으로 분해하였으며, 분해 생성된 리그닌오일의 물리화학적 특성을 다양한 분석방법을 이용하여 조사하였다. 리그닌오일의 수율은 반응온도가 $250^{\circ}C$에서 $350^{\circ}C$로 상승함에 따라 89.5 wt%에서 32.1 wt%로 감소하는 경향을 보였지만 분자량 및 다분산지수는 $350^{\circ}C$ 조건에서 아시안 리그닌(3698Da, 2.68) 대비 각각 85%, 44% 감소하여 효과적인 탈중합 반응이 진행되었음을 확인할 수 있었다. 리그닌오일의 GC/MS 분석 결과 guaiacol, 4-ethylphenol, 4-methylguaiacol, syringol, and 4-methysyringol 등 단량체 수준의 페놀화합물은 반응온도가 증가할수록 24.1 mg/g of lignin ($250^{\circ}C$)에서 64.8 mg/g of lignin ($350^{\circ}C$)으로 증가하였으며, 반응기 내부에 수소가스와 촉매(Ru/C)를 첨가하였을 때 최대 76.1 mg/g of lignin 수준까지 향상되는 것을 확인할 수 있었다. 한편 리그닌오일의 원소분석 결과 반응온도가 증가함에 따라 탄소함량은 증가한 반면 산소함량은 점차 감소하였으며, 이를 통해 아시안 리그닌 탈중합 공정 중 수첨탈산소반응 및 수소첨가반응이 진행됨을 간접적으로 확인할 수 있었다.

Keywords

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