화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Journal of Chemical Engineering, Vol.38, No.6, 1079-1086, June, 2021
DOI10.1007/s11814-020-0725-9  Export Citation
Catalytic production of hexamethylenediamine from renewable feedstocks
Jechan Lee1, 2, †, Younghyun Lee1, Soosan Kim1, Eilhann E. Kwon3, and Kun-Yi Andrew Lin4, †
  • 1Department of Environmental Engineering, Ajou University, 206 Worldcup-ro, Suwon 16499, Korea
  • 2Department of Energy Systems Research, Ajou University, 206 Worldcup-ro, Suwon 16499, Korea
  • 3Department of Environment and Energy, Sejong University, 209 Neungdong-ro, Seoul 05006, Korea
  • 4Department of Environmental Engineering & Innovation and Development Center of Sustainable Agriculture, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung, Taiwan
E-mail:,
Renewable biomass-derived chemicals have received considerable interest as a potential substitute for petroleum-derived chemicals. Hexamethylenediamine is a key intermediate in manufacturing nylon 66, a synthetic polymer that is broadly used in society. This article reviews the catalytic production of hexamethylenediamine from biomass-derived chemical feedstocks, and specifically the bio-based routes for obtaining hexamethylenediamine. While methods to directly convert biomass to hexamethylenediamine have yet to be commercialized, the use of heterogeneous catalytic systems via combined processes appears to be a promising and emerging chemical pathway to achieve this goal. Current proposed routes for the renewable production of hexamethylenediamine are not yet entirely competitive with petrochemical production techniques, predominantly because of low efficiency and high cost. However, many opportunities exist to advance technologies that exploit renewable and bio-based feedstocks to generate hexamethylenediamine. Thus, the commercialization of biomass-derived nylon monomers appears achievable in the near future.
Keywords:Adiponitrile;Biomass;Biorefinery;Heterogeneous Catalyst;Hydrogenation;Nylon
  1. Wittcoff HA, Reuben BG, Plotkin JS, Industrial organic chemicals, (2013).
  2. Song W, Wang S, Xu D, Guo Y, Yang C, Zhang J, Li Y, Korean J. Chem. Eng., 36(10), 1604 (2019)
  3. Kim S, Kwon EE, Kim YT, Jung S, Kim HJ, Huber GW, Lee J, Green Chem., 21, 3715 (2019)
  4. Wang Z, Fu Z, Lin W, Li S, Song W, Korean J. Chem. Eng., 36(8), 1235 (2019)
  5. Lee HW, Jeong HS, Ju YM, Lee SM, Korean J. Chem. Eng., 37(7), 1174 (2020)
  6. AbdelSalam H, El-Maghrbi HH, Zahran F, Zaki T, Korean J. Chem. Eng., 37(4), 670 (2020)
  7. Park C, Lee J, Green Chem., 22, 2628 (2020)
  8. Pham HM, Kang MJ, Kim KA, Im CG, Hwang SY, Cha HG, Korean J. Chem. Eng., 37(3), 556 (2020)
  9. Dikshit PK, Jun HB, Kim BS, Korean J. Chem. Eng., 37(3), 387 (2020)
  10. Purnama A, Wijaya K, Tahir I, Suyono EA, Budiman A, Korean J. Chem. Eng., 37(3), 466 (2020)
  11. Si Z, Zhang X, Zuo M, Wang T, Sun Y, Tang X, Zeng X, Lin L, Korean J. Chem. Eng., 37(2), 224 (2020)
  12. Holbery J, Houston D, JOM, 58, 80 (2006)
  13. Papadopoulou EL, Pignatelli F, Marras S, Marini L, Davis A, Athanassiou A, Bayer IS, RSC Adv., 6, 6823 (2016)
  14. Pan G, Zhao Y, Xu H, Hou X, Yang Y, J. Clean Prod., 117, 212 (2016)
  15. Weissermel K, Arpe HJ, Industrial organic chemistry, Wiley-VCH, Weinheim (2003).
  16. Maximize Market Research, https://www.maximizemarketresearch.com/market (2019).
  17. Botelho EC, Scherbakoff N, Rezende MC, Kawamoto AM, Sciamareli J, Macromolecules, 34(10), 3367 (2001)
  18. Pelckmans M, Renders T, Van de Vyver S, Sels BF, Green Chem., 19, 5303 (2017)
  19. Balladur V, Fouilloux P, Debellefon C, Appl. Catal. A: Gen., 133(2), 367 (1995)
  20. Lee Y, Lee SW, Kim HJ, Kim YT, Lin KYA, Lee J, Appl. Sci., 10, 7506 (2020)
  21. Li H, Xu Y, Deng JF, New J. Chem., 23, 1059 (1999)
  22. Harper MJ, United States Patent, US6156694A (2000).
  23. Yu XB, Li HX, Deng JF, Appl. Catal. A: Gen., 199(2), 191 (2000)
  24. Li HX, Xu YP, Li H, Deng JF, Appl. Catal. A: Gen., 216(1-2), 51 (2001)
  25. Medina F, Salagre P, Sueiras JE, Fierro JLG, J. Mol. Catal., 81, 387 (1993)
  26. Jia Z, Zhen B, Han M, Wang C, Catal. Commun., 73, 80 (2016)
  27. Wang C, Jia Z, Zhen B, Han M, Molecules, 23, 92 (2018)
  28. Liao H, Liu S, Hao F, Liu P, You K, Liu D, Luo HA, React. Kinet. Catal. Lett., 109, 475 (2013)
  29. Liu S, Hao F, Liu P, Luo HA, Liao H, Res. Chem. Intermed., 41, 5879 (2015)
  30. Lv Y, Hao F, Xiong S, Liu P, Luo HA, RSC Adv., 6, 60933 (2016)
  31. Lv Y, Hao F, Liu P, Xiong S, Luo H, React. Kinet. Mech. Catal., 119, 555 (2016)
  32. Lv Y, Hao F, Liu PL, Xiong SF, Luo HA, J. Mol. Catal. A-Chem., 426, 15 (2017)
  33. Lv Y, Li J, Feng S, Liu PL, Hao F, Xiong W, Luo HA, Chem. Eng. J., 346, 203 (2018)
  34. Alini S, Bottino A, Capannelli G, Carbone R, Comite A, Vitulli G, J. Mol. Catal. A-Chem., 206(1-2), 363 (2003)
  35. Wilson K, Adams DJ, Rothenberg G, Clark JH, J. Mol. Catal. A-Chem., 159(2), 309 (2000)
  36. Gallezot P, Chem. Soc. Rev., 41, 1538 (2012)
  37. Sheldon RA, Green Chem., 16, 950 (2014)
  38. Pacheco JJ, Davis ME, Proc. Natl. Acad. Sci. USA, 111, 8363 (2014)
  39. Beerthuis R, Rothenberg G, Shiju NR, Green Chem., 17, 1341 (2015)
  40. Lee Y, Kwon EE, Lee J, Rev. Environ. Sci. Biotechnol., 18, 317 (2019)
  41. Lee Y, Lin KYA, Kwon EE, Lee J, J. Clean Prod., 227, 624 (2019)
  42. Cole-Hamilton DJ, Science, 299, 1702 (2003)
  43. Dev A, Srivastava AK, Karmakar S, Handbook of nanomaterials for industrial applications, 217 (2018).
  44. Matthieu C, Dietrich E, Delmas H, Jenck J, Chem. Eng. Sci., 47, 2289 (1992)
  45. Jolyvuillemin C, Gavroy D, Cordier G, Debellefon C, Delmas H, Chem. Eng. Sci., 49(24), 4839 (1994)
  46. Rostrup-Nielsen JR, Science, 308, 1421 (2005)
  47. Goldemberg J, Science, 315, 808 (2007)
  48. Zhang MH, Yu YZ, Ind. Eng. Chem. Res., 52(28), 9505 (2013)
  49. Angelici C, Weckhuysen BM, Bruijnincx PCA, ChemSusChem, 6, 1595 (2013)
  50. Makshina EV, Dusselier M, Janssens W, Degreve J, Jacobs PA, Sels BF, Chem. Soc. Rev., 43, 7917 (2014)
  51. Ohnishi R, Akimoto T, Tanabe K, J. Chem. Soc., Chem. Commun., 1613 (1985).
  52. Chieregato A, Ochoa JV, Bandinelli C, Fornasari G, Cavani F, Mella M, ChemSusChem, 8, 377 (2015)
  53. Ochoa JV, Bandinelli C, Vozniuk O, Chieregato A, Malmusi A, Recchi C, Cavani F, Green Chem., 18, 1653 (2016)
  54. Pomalaza G, Capron M, Ordomsky V, Dumeignil F, Catalysts, 6, 203 (2016)
  55. Kyriienko PI, Larina OV, Soloviev SO, Orlyk SM, Calers C, Dzwigaj S, ACS Sustainable Chem. Eng., 5, 2075 (2017)
  56. Wang Z, Comprehensive organic name reactions and reagents, USA, 1728 (2010).
  57. Zeitsch KJ, The chemistry and technology of furfural and its many by-products, The Netherlands (2000).
  58. Lange JP, van der Heide E, van Buijtenen J, Price R, ChemSusChem, 5, 150 (2012)
  59. Choudhary H, Nishimura S, Ebitani K, Chem. Lett., 41(4), 409 (2012)
  60. Choudhary H, Nishimura S, Ebitani K, Appl. Catal. A: Gen., 458, 55 (2013)
  61. Deshpande RM, Buwa VV, Rode CV, Chaudhari RV, Mills PL, Catal. Commun., 3, 269 (2002)
  62. Ly BK, Minh DP, Pinel C, Besson M, Tapin B, Epron F, Especel C, Top. Catal., 55, 466 (2012)
  63. Chung SH, Park YM, Kim MS, Lee KY, Catal. Today, 185(1), 205 (2012)
  64. Ly BK, Tapin B, Aouine M, Delichere P, Epron F, Pinel C, Especel C, Besson M, ChemCatChem, 7, 2161 (2015)
  65. Kang KH, Hong UG, Bang Y, Choi JH, Kim JK, Lee JK, Han SJ, Song IK, Appl. Catal. A: Gen., 490, 153 (2015)
  66. Zhang W, Zhu YL, Niu S, Li YW, J. Mol. Catal. A-Chem., 335(1-2), 71 (2011)
  67. Pushkarev VV, Musselwhite N, An K, Alayoglu S, Somorjai GA, Nano Lett., 12, 5196 (2012)
  68. An K, Musselwhite N, Kennedy G, Pushkarev VV, Baker LR, Somorjai GA, J. Colloid Interface Sci., 392, 122 (2013)
  69. Ishida T, Kume K, Kinjo K, Honma T, Nakada K, Ohashi H, et al., ChemSusChem, 9, 3441 (2016)
  70. Fischer R, Pinkos R, United States Patent, US5905159A (1999).
  71. Vecchini N, Galeotti A, Pisano A, International Patent, WO2016092517A1 (2016).
  72. Wang YC, Sun DL, Yamada Y, Sato S, Appl. Catal. A: Gen., 562, 11 (2018)
  73. Richard R, Jacquin M, Dorato M, Pacheco N, Rannoux C, United States Patent, US10322978B2 (2019).
  74. Sato F, Sato S, Yamada Y, Nakamura M, Shiga A, Catal. Today, 226, 124 (2014)
  75. Nakagawa Y, Kasumi T, Ogihara J, Tamura M, Arai T, Tomishige K, ACS Omega, 5, 2520 (2020)
  76. Childers KG, Dreher SD, Lee J, Williams JM, Org. Process Res. Dev., 10, 934 (2006)
  77. Liu L, Asano T, Nakagawa Y, Tamura M, Tomishige K, Green Chem., 22, 2375 (2020)
  78. Jing F, Katryniok B, Araque M, Wojcieszak R, Capron M, et al., Catal. Sci. Technol., 6, 530 (2016)
  79. Decker M, Schmidt J, Hoffmann H, Pistor HJ, United States Patent, US3671566A (1972).
  80. Shi J, Zhang X, Chen G, Fan L, Shu C, Dang G, Zhan X, et al., China Patent, CN106146345B (2018).
  81. Musser MT, “Adipic acid”, Ullmann’s encyclopedia of industrial chemistry, Wiley-VCH, Weinheim (2000).
  82. Blanco DE, Dookhith AZ, Modestino MA, React. Chem. Eng., 4, 8 (2019)
  83. Dai JJ, Huang YB, Fang C, Guo QX, Fu Y, ChemSusChem, 5, 617 (2012)
  84. Werpy T, Petersen G, Top value added chemicals from biomass: Volume 1 - results of screening for potential candidates from sugars and synthetic gas, (20014).
  85. Baldwin JE, North M, Flinn A, Moloney MG, Tetrahedron, 45, 1453 (1989)
  86. de Bellefon C, Fouilloux P, Catal. Rev.-Sci. Eng., 36, 459 (1994)
  87. Howk BW, United States Patent, US2166151A (1939).
  88. Augustine RL, Catal. Rev.-Sci. Eng., 13, 285 (1976).
  89. Herzog BD, Smiley RA, “Hexamethylenediamine”, Ullmann’s encyclopedia of industrial chemistry (2012).
  90. Sengupta SK, Koch TA, Krause KR, United States Patent, US5900511A (1999).
  91. Lv Y, Cui HS, Liu PL, Hao F, Xiong W, Luo HA, J. Catal., 372, 330 (2019)
  92. Gilkey MJ, Xu B, ACS Catal., 6, 1420 (2016)
  93. Liu H, Guo Y, Yu Y, Yang W, Shen M, Liu X, Geng S, Li J, Yu C, Yin Z, Li H, J. Mater. Chem. A, 6, 17323 (2018)
  94. Serra M, Salagre P, Cesteros Y, Medina F, Sueiras JE, J. Catal., 209(1), 202 (2002)
  95. van Putten RJ, van der Waal JC, de Jong E, Rasrendra CB, Heeres HJ, de Vries JG, Chem. Rev., 113(3), 1499 (2013)
  96. Nikolla E, Roman-Leshkov Y, Moliner M, Davis ME, ACS Catal., 1, 408 (2011)
  97. Pagan-Torres YJ, Wang T, Gallo JMR, Shanks BH, Dumesic JA, ACS Catal., 2, 930 (2012)
  98. Xu S, Yin C, Pang D, Hu F, Wu Y, Miao Y, Gao L, Xiao G, Sustain. Energy Fuels, 3, 390 (2019)
  99. Buntara T, Noel S, Phua PH, Melian-Cabrera I, Vries JGD, Heeres HJ, Angew. Chem.-Int. Edit., 50, 7083 (2011)
  100. Dias EL, Shoemaker JAW, Boussie TR, Murphy VJ, United States Patent, US9518005B2 (2016).
  101. Horlenko T, Tatum HW, United States Patent, 3,215,742 (1965).
  102. Muller C, et al., United States Patent, US20160326092A1 (2016).
  103. Dros AB, Larue O, Reimond A, De Campo F, Pera-Titus M, Green Chem., 17, 4760 (2015)
  104. Thaore V, Chadwick D, Shah N, Chem. Eng. Res. Des., 135, 140 (2018)
  105. Kim SS, Tsang YF, Kwon EE, Lin KYA, Lee JC, Korean J. Chem. Eng., 36(1), 1 (2019)
  106. Park YK, Ha JM, Oh S, Lee J, Chem. Eng. J., 404, 126527 (2021)
  107. Han J, Kim Y, Jackson DHK, Chang H, Kim HW, Lee J, et al., Appl. Catal. B: Environ., 273, 119037 (2020)