화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Applied Chemistry for Engineering, Vol.27, No.2, 135-144, April, 2016
DOI10.14478/ace.2016.1016  Export Citation
목질계 바이오매스 전처리 공정에서 발생하는 리그닌 부산물 활용 기술 개발 동향
Value-added Utilization of Lignin Residue from Pretreatment Process of Lignocellulosic Biomass
정재영, 이유미, 이은열†
  • 경희대학교 공과대학 화학공학과
Jae Yeong Jung, Yumi Lee, and Eun Yeol Lee†
  • Department of chemical engineering, Kyung Hee University, Gyeonggi-do 17104, Korea
E-mail:
초록
불안정한 원유 가격과 지속적인 환경 문제를 야기하고 있는 석유 자원의 대체를 위한 바이오매스 활용 기술 개발과 상업화가 활발히 진행되고 있다. 목질계 바이오매스 전처리와 펄프 제조 과정에서 다량으로 발생하는 리그닌은 바이오에탄올 제조량의 증가와 더불어 발생량 또한 급속히 증가할 것으로 예상되고 있다. 리그닌은 방향족 고분자로 hydroxyl기와 같은 화학 작용기를 갖고 있어 화학 소재 원료로서의 활용이 가능한 저가 부산물이다. 리그닌의 방향족 구조와 작용기를 oxypropylation, epxoidation 등을 이용하여 화학적으로 변환시켜 반응성을 향상시키거나, 새로운 화학작용기를 도입함으로써 바이오폴리우레탄, 바이오폴리에스터, 페놀 수지, 에폭시 수지 등 바이오플라스틱 제조에 활용이 가능하다. 본 총설은 리그닌을 활용하여 제조 가능한 바이오플라스틱, 수지, 탄소섬유 등에 대해 소개하고, 관련 최신 연구 동향 및 리그닌 응용 기술에 관한 전망을 소개하였다.
Due to the high price volatility and environmental concern of petroleum, biofuels such as bioethanol produced from lignocellulosic biomass have attracted much attention. It is also expected that the amount of lignin residue generated from pretreatment of lignocellulosic biomass will increase as the volume of cellulosic bioethanol increases. Lignin is a natural aromatic polymer and has very complex chemical structures with chemical functional groups. Chemical modification of lignin such as oxypropylation and epoxidation has also been applied to the production of value-added bioplastics such as polyurethane and polyester with enhanced thermal and mechanical properties. In addition, lignin can be used for carbon fiber production in automobile industries. This review highlights recent progresses in utilizations and chemical modifications of lignin for the production of bioplastics, resins, and carbon fiber.
Keywords:lignin;lignocellulosic biomass;bioplastics;chemical modification;carbon fiber
  1. Eom HJ, Hong YK, Chung SH, Park YM, Lee KY, J. Energy Eng., 20, 36 (2011)
  2. Melero JA, Iglesias J, Garcia A, Energy Environ. Sci., 5, 7393 (2012)
  3. Zhu JY, Pan XJ, Bioresour. Technol., 101(13), 4992 (2010)
  4. Ballesteros M, Oliva JM, Negro MJ, Manzanares P, Ballesteros I, Process Biochem., 39(12), 1843 (2004)
  5. Lei ZP, Hu ZQ, Shui HF, Ren SB, Wang ZC, Kang SG, Pan CX, Fuel Process. Technol., 138, 612 (2015)
  6. Kubo S, Kadla JF, J. Polym. Environ., 13, 97 (2005)
  7. Kleinert M, Barth T, Chem. Eng. Technol., 31(5), 736 (2008)
  8. Luo X, Mohanty A, Misra M, Ind. Crop. Prod., 47, 13 (2013)
  9. Sen S, Patil S, Argyropoulos DS, Green Chem., 17, 4862 (2015)
  10. Dorrestijn E, Laarhoven LJ, Arends IW, Mulder P, J. Anal. Appl. Pyrolysis, 54, 153 (2000)
  11. Sangha AK, Parks JM, Standaert RF, Ziebell A, Davis M, Smith JC, J. Phys. Chem. B, 116(16), 4760 (2012)
  12. Chakar FS, Ragauskas AJ, Ind. Crop. Prod., 20, 131 (2004)
  13. Azadi P, Inderwildi OR, Farnood R, King DA, Renew. Sust. Energ. Rev., 21, 506 (2013)
  14. Laurichesse S, Averous L, Prog. Polym. Sci, 39, 1266 (2014)
  15. Lee A, Deng Y, Eur. Polym. J., 63, 67 (2015)
  16. Park Y, Doherty WO, Halley PJ, Ind. Crop. Prod., 27, 163 (2008)
  17. Zhao BY, Chen G, Liu Y, Hu K, Wu RJ, J. Mater. Sci. Lett., 20(9), 859 (2001)
  18. Jo YJ, Choi SH, Lee EY, Appl. Chem. Eng., 24(6), 579 (2013)
  19. Hatakeyema H, Tanamachi N, Matsumura H, Hirose S, Hatakeyama T, Thermochim. Acta, 431, 155 (2005)
  20. Auvergne R, Caillol S, David G, Boutevin B, Pascault JP, Chem. Rev., 114, 1082 (2013)
  21. Pilato L, React. Funct. Polym., 73(2), 270 (2013)
  22. Kim KH, Jo YJ, Lee CG, Lee EY, Algal Res., 12, 539 (2015)
  23. Nakamura K, Hatakeyama T, Hatakeyama H, Polym. Adv. Technol., 3, 151 (1992)
  24. Hu SJ, Wan CX, Li YB, Bioresour. Technol., 103(1), 227 (2012)
  25. Li Y, Ragauskas AJ, J. Wood Chem. Technol., 32, 210 (2012)
  26. Mahmood N, Yuan ZS, Schmidt J, Xu CB, Bioresour. Technol., 139, 13 (2013)
  27. Hu S, Luo X, Li Y, Chem. Sus. Chem., 7, 66 (2014)
  28. da Silva EAB, Zabkova M, Araujo JD, Cateto CA, Barreiro MF, Belgacem MN, Rodriques AE, Chem. Eng. Res. Des., 87(9A), 1276 (2009)
  29. Jin YQ, Ruan XM, Cheng XS, Lu QF, Bioresour. Technol., 102(3), 3581 (2011)
  30. Li HQ, Shao Q, Luo H, Xu J, J. Appl. Polym. Sci., Doi:10.1002/app.43261.
  31. Lee JH, Lee JH, Kim DK, Park CH, Yu JH, Lee EY, J. Ind. Eng. Chem., 34, 157 (2016)
  32. Dominguez JC, Oliet M, Alonso MV, Rojo E, Rodriguez F, Ind. Crop. Prod., 42, 308 (2013)
  33. Perez JM, Oliet M, Alonso MV, Rodriguez F, Thermochim. Acta, 487(1-2), 39 (2009)
  34. Cheng S, Yuan Z, Leitch M, Anderson M, Xu CC, Ind. Crop. Prod., 44, 315 (2013)
  35. Cetin NS, Ozmen N, Int. J. Adhes. Adhes., 22, 477 (2002)
  36. Alonso MV, Oliet A, Perez JM, Rodriguez F, Echeverria J, Thermochim. Acta, 419(1-2), 161 (2004)
  37. Lin CC, Teng HS, Ind. Eng. Chem. Res., 41(8), 1986 (2002)
  38. Pal PK, Kumar A, Gupta SK, Polymer, 22, 1699 (1981)
  39. Lee WJ, Chang KC, Tseng IM, J. Appl. Polym. Sci., 124(6), 4782 (2012)
  40. Zhang W, Ma Y, Xu Y, Wang C, Chu F, Int. J. Adhes. Adhes., 40, 11 (2013)
  41. Lee WJ, Chen YC, Bioresour. Technol., 99(15), 7247 (2008)
  42. Raquez JM, Deleglise M, Lacrampe MF, Krawczak P, Prog. Polym. Sci, 35, 487 (2010)
  43. Anderson BJ, Polym. Degrad. Stabil., 96, 1874 (2011)
  44. Bagherzadeh MR, Daneshvar A, Shariatpanahi H, Surf. Coat. Technol., 206, 2057 (2012)
  45. Yang TI, Peng CW, Lin YL, Weng CJ, Edgington G, Mylonakis A, Huang TC, Hsu CH, Yeh JM, Wei Y, J. Mater. Chem., 22, 15845 (2012)
  46. Li K, Wang K, Zhan MS, Xu W, Polym. Degrad. Stabil., 98, 2340 (2013)
  47. Fischer RF, J. Polym. Sci., 44, 155 (1960)
  48. Sinh LH, Trung NN, Son BT, Shin S, Thanh DT, Bae JY, Polym. Eng. Sci., 54(3), 695 (2014)
  49. Dodds EC, Lawson W, Nature, 137, 996 (1936)
  50. Howdeshell KL, Hotchkiss AK, Thayer KA, Vandenbergh JG, VomSaal FS, Nature, 401, 763 (1999)
  51. Campanella A, Baltanas MA, Capel-Sanchez MC, Campos-Martin JM, Fierro JLG, Green Chem., 6, 330 (2004)
  52. Koike T, Polym. Eng. Sci., 52(4), 701 (2012)
  53. El Mansouri NE, Yuan Q, Huang F, Bioresources, 6, 2492 (2011)
  54. Malutan T, Nicu R, Popa VI, Bioresources, 3, 1371 (2008)
  55. Eom HJ, Hong YK, Chung SH, Park YM, Lee KY, J. Energy Eng., 20, 36 (2011)
  56. Melero JA, Iglesias J, Garcia A, Energy Environ. Sci., 5, 7393 (2012)
  57. Zhu JY, Pan XJ, Bioresour. Technol., 101(13), 4992 (2010)
  58. Ballesteros M, Oliva JM, Negro MJ, Manzanares P, Ballesteros I, Process Biochem., 39(12), 1843 (2004)
  59. Lei ZP, Hu ZQ, Shui HF, Ren SB, Wang ZC, Kang SG, Pan CX, Fuel Process. Technol., 138, 612 (2015)
  60. Kubo S, Kadla JF, J. Polym. Environ., 13, 97 (2005)
  61. Kleinert M, Barth T, Chem. Eng. Technol., 31(5), 736 (2008)
  62. Luo X, Mohanty A, Misra M, Ind. Crop. Prod., 47, 13 (2013)
  63. Sen S, Patil S, Argyropoulos DS, Green Chem., 17, 4862 (2015)
  64. Dorrestijn E, Laarhoven LJ, Arends IW, Mulder P, J. Anal. Appl. Pyrolysis, 54, 153 (2000)
  65. Sangha AK, Parks JM, Standaert RF, Ziebell A, Davis M, Smith JC, J. Phys. Chem. B, 116(16), 4760 (2012)
  66. Chakar FS, Ragauskas AJ, Ind. Crop. Prod., 20, 131 (2004)
  67. Azadi P, Inderwildi OR, Farnood R, King DA, Renew. Sust. Energ. Rev., 21, 506 (2013)
  68. Laurichesse S, Averous L, Prog. Polym. Sci, 39, 1266 (2014)
  69. Lee A, Deng Y, Eur. Polym. J., 63, 67 (2015)
  70. Park Y, Doherty WO, Halley PJ, Ind. Crop. Prod., 27, 163 (2008)
  71. Zhao BY, Chen G, Liu Y, Hu K, Wu RJ, J. Mater. Sci. Lett., 20(9), 859 (2001)
  72. Jo YJ, Choi SH, Lee EY, Appl. Chem. Eng., 24(6), 579 (2013)
  73. Hatakeyema H, Tanamachi N, Matsumura H, Hirose S, Hatakeyama T, Thermochim. Acta, 431, 155 (2005)
  74. Auvergne R, Caillol S, David G, Boutevin B, Pascault JP, Chem. Rev., 114, 1082 (2013)
  75. Pilato L, React. Funct. Polym., 73(2), 270 (2013)
  76. Kim KH, Jo YJ, Lee CG, Lee EY, Algal Res., 12, 539 (2015)
  77. Nakamura K, Hatakeyama T, Hatakeyama H, Polym. Adv. Technol., 3, 151 (1992)
  78. Hu SJ, Wan CX, Li YB, Bioresour. Technol., 103(1), 227 (2012)
  79. Li Y, Ragauskas AJ, J. Wood Chem. Technol., 32, 210 (2012)
  80. Mahmood N, Yuan ZS, Schmidt J, Xu CB, Bioresour. Technol., 139, 13 (2013)
  81. Hu S, Luo X, Li Y, Chem. Sus. Chem., 7, 66 (2014)
  82. da Silva EAB, Zabkova M, Araujo JD, Cateto CA, Barreiro MF, Belgacem MN, Rodriques AE, Chem. Eng. Res. Des., 87(9A), 1276 (2009)
  83. Jin YQ, Ruan XM, Cheng XS, Lu QF, Bioresour. Technol., 102(3), 3581 (2011)
  84. Li HQ, Shao Q, Luo H, Xu J, J. Appl. Polym. Sci., Doi:10.1002/app.43261.
  85. Lee JH, Lee JH, Kim DK, Park CH, Yu JH, Lee EY, J. Ind. Eng. Chem., 34, 157 (2016)
  86. Dominguez JC, Oliet M, Alonso MV, Rojo E, Rodriguez F, Ind. Crop. Prod., 42, 308 (2013)
  87. Perez JM, Oliet M, Alonso MV, Rodriguez F, Thermochim. Acta, 487(1-2), 39 (2009)
  88. Cheng S, Yuan Z, Leitch M, Anderson M, Xu CC, Ind. Crop. Prod., 44, 315 (2013)
  89. Cetin NS, Ozmen N, Int. J. Adhes. Adhes., 22, 477 (2002)
  90. Alonso MV, Oliet A, Perez JM, Rodriguez F, Echeverria J, Thermochim. Acta, 419(1-2), 161 (2004)
  91. Lin CC, Teng HS, Ind. Eng. Chem. Res., 41(8), 1986 (2002)
  92. Pal PK, Kumar A, Gupta SK, Polymer, 22, 1699 (1981)
  93. Lee WJ, Chang KC, Tseng IM, J. Appl. Polym. Sci., 124(6), 4782 (2012)
  94. Zhang W, Ma Y, Xu Y, Wang C, Chu F, Int. J. Adhes. Adhes., 40, 11 (2013)
  95. Lee WJ, Chen YC, Bioresour. Technol., 99(15), 7247 (2008)
  96. Raquez JM, Deleglise M, Lacrampe MF, Krawczak P, Prog. Polym. Sci, 35, 487 (2010)
  97. Anderson BJ, Polym. Degrad. Stabil., 96, 1874 (2011)
  98. Bagherzadeh MR, Daneshvar A, Shariatpanahi H, Surf. Coat. Technol., 206, 2057 (2012)
  99. Yang TI, Peng CW, Lin YL, Weng CJ, Edgington G, Mylonakis A, Huang TC, Hsu CH, Yeh JM, Wei Y, J. Mater. Chem., 22, 15845 (2012)
  100. Li K, Wang K, Zhan MS, Xu W, Polym. Degrad. Stabil., 98, 2340 (2013)
  101. Fischer RF, J. Polym. Sci., 44, 155 (1960)
  102. Sinh LH, Trung NN, Son BT, Shin S, Thanh DT, Bae JY, Polym. Eng. Sci., 54(3), 695 (2014)
  103. Dodds EC, Lawson W, Nature, 137, 996 (1936)
  104. Howdeshell KL, Hotchkiss AK, Thayer KA, Vandenbergh JG, VomSaal FS, Nature, 401, 763 (1999)
  105. Campanella A, Baltanas MA, Capel-Sanchez MC, Campos-Martin JM, Fierro JLG, Green Chem., 6, 330 (2004)
  106. Koike T, Polym. Eng. Sci., 52(4), 701 (2012)
  107. El Mansouri NE, Yuan Q, Huang F, Bioresources, 6, 2492 (2011)
  108. Malutan T, Nicu R, Popa VI, Bioresources, 3, 1371 (2008)
  109. Kuo PY, Sain M, Yan N, Green Chem., 16, 3483 (2014)
  110. Pan H, Sun G, Zhao T, Int. J. Biol. Macromol., 59, 221 (2013)
  111. Sasaki C, Wanaka M, Takagi H, Tamura S, Asada C, Nakamura Y, Ind. Crop. Prod., 43, 757 (2013)
  112. Ferdosian F, Yuan Z, Anderson M, Xu CC, RSC Adv., 4, 31745 (2014)
  113. Ferdosian F, Yuan ZS, Anderson M, Xu CB, Thermochim. Acta, 618, 48 (2015)
  114. Qin J, Woloctt M, Zhang J, ACS Sustain. Chem. Eng., 2, 188 (2013)
  115. Saito T, Brown RH, Hunt MA, Pickel DL, Pickel JM, Messman JM, Baker FS, Keller M, Naskar AK, Green Chem., 14, 3295 (2012)
  116. Korich AL, Clarke KM, Wallace D, Lovine PM, Macromolecules, 42(16), 5906 (2009)
  117. Lora JH, Glasser WG, J. Polym. Environ., 10, 39 (2002)
  118. Evtiouguina M, Barros-Timmons A, Cruz-Pinto JJ, Neto CP, Belgacem MN, Gandini A, Biomacromolecules, 3(1), 57 (2002)
  119. Ahvazi B, Wojciechowicz O, Ton-That TM, Hawari J, J. Agric. Food Chem., 59, 10505 (2011)
  120. Cateto CA, Barreiro MF, Rodrigues AE, Belgacem MN, Ind. Eng. Chem. Res., 48(5), 2583 (2009)
  121. Nadji H, Bruzzese C, Belgacem MN, Benaboura A, Gandini A, Macromol. Mater. Eng., 290, 1009 (2005)
  122. Sadeghifar H, Cui CZ, Argyropoulos DS, Ind. Eng. Chem. Res., 51(51), 16713 (2012)
  123. Yoshioka M, Nishio Y, Saito D, Ohashi H, Hashimoto M, Shiraishi N, J. Appl. Polym. Sci., 130(1), 622 (2013)
  124. Alonso MV, Oliet M, Rodriguez F, Garcia J, Gilarranz MA, Rodriguez JJ, Bioresour. Technol., 96(9), 1013 (2005)
  125. Hu L, Pan H, Zhou Y, Zhang M, BioResources, 6, 3515 (2011)
  126. Podschun J, Saake B, Lehnen R, Eur. Polym. J., 67, 1 (2015)
  127. Fang R, Cheng X, Lin WS, BioResources, 6, 2874 (2011)
  128. Qiao J, Guo M, Wang L, Liu D, Zhang X, Yu L, Song W, Liu Y, Polym. Chem., 2, 1611 (2011)
  129. Chung H, Washburn NR, Green Mat., 1, 137 (2012)
  130. Mikulasova M, Kosikova B, Alexy P, Kacik F, Urgelov E, World J. Microbiol. Biotechnol., 17, 601 (2001)
  131. Cazacu G, Pascu MC, Profire L, Kowarski AI, Mihaes M, Vasile C, Ind. Crop. Prod., 20, 261 (2004)
  132. Nahmany M, Melman A, Org. Biomol. Chem., 2, 1563 (2004)
  133. Sivasankarapillai G, McDonald AG, Li H, Biomass Bioenerg., 47, 99 (2012)
  134. Saito T, Brown RH, Hunt MA, Pickel DL, Pickel JM, Messman JM, Baker FS, Keller M, Naskar AK, Green Chem., 14, 3295 (2012)
  135. Guo ZX, Gandini A, Eur. Polym. J., 27, 1177 (1991)
  136. Binh NTT, Luong ND, Kim DO, Lee SH, Kim BJ, Lee YS, Nam JD, Compos. Interfaces, 16(7-9), 923 (2009)
  137. Frank E, Steudle LM, Ingildeev D, Sporl JM, Buchmeiser MR, Angew. Chem.-Int. Edit., 53, 5262 (2014)
  138. Norberg I, Nordstrom Y, Drougge R, Gellerstedt G, Sjoholm E, J. Appl. Polym. Sci., 128(6), 3824 (2013)
  139. Kadla JF, Kubo S, Venditti RA, Gilbert RD, Compere AL, Griffith W, Carbon, 40, 2913 (2002)
  140. Baker DA, Rials TG, J. Appl. Polym. Sci., 130(2), 713 (2013)
  141. Gellerstedt G, Sjoholm E, Brodin I, Open Agric. J., 4, 119 (2010)