화학공학소재연구정보센터
Journal of Industrial and Engineering Chemistry, Vol.111, 369-379, July, 2022
Lignin-based sulfonated carbon as an efficient biomass catalyst for clean benzylation of benzene ring compounds
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Low-temperature carbonization–sulfonation two-step process or one-step sulfonation process was employed to draft sodium lignosulfonate (SLS), the primary biological macromolecule ingredient of papermaking black liquor, into lignin-based sulfonated carbon. The two-step lignin-based sulfonated carbon named SLC400,1S was found to be an efficient catalyst for clean Benzyl-alcohol (BA) route Friedel-Crafts (F-C) benzylation of benzene ring compounds. FT-IR, XRD, Raman spectra, XPS, SEM with EDXmapping, TGA-DSC, acid-base titration, and n-butylamine–acetonitrile titration characterizations demonstrated that the specific two-step process could introduce porous properties and a large number of surface sulfonic, hydroxyl, and carboxyl active groups into the structure of the prepared material, which was found to account for the good catalytic performance for benzylation. Similar to that of hierarchical mesoporous ZSM-5 under optimal conditions, the apparent activation energy for benzylation of paraxylene (PX) with BA over SLC400,1S was estimated to be 119 kJ·mol-1. The common by-product of BA route benzylation, dibenzyl ether (DBE), was almost inhibited because of the extraordinary activity of SLC400,1S and the optimized reaction conditions. A 12-run recycling test demonstrated easy recovery and steady reusability of the above lignin-based sulfonated carbon catalyst.
  1. Zimmerman JB, Anastas PT, Erythropel HC, Leitner W, Science, 367, 397 (2020)
  2. Schmidt F, Stemmler RT, Rudolph J, Bolm C, Chem. Soc. Rev., 35, 454 (2006)
  3. Iovel I, Mertins K, Kischel J, Zapf A, Beller M, Angew. Chem.-Int. Edit., 44(25), 3913 (2005)
  4. Bandini M, Melloni A, Umani-Ronchi A, Angew. Chem.-Int. Edit., 43(5), 550 (2004)
  5. Alberico D, Scott ME, Lautens M, Chem. Rev., 107(1), 174 (2007)
  6. Ghiaci M, Abbaspur A, Kia R, Belver C, Trujillano R, Rives V, et al., Catal. Commun., 8(1), 49 (2007)
  7. Bokade VV, Yadav GD, J. Nat. Gas Chem., 16(2), 186 (2007)
  8. Deshpande AB, Bajpai AR, Samant SD, Appl. Catal. A: Gen., 209, 229 (2001)
  9. Li Q, Jiang S, Ji S, Shi DA, Li H, J. Porous Mat., 22(5), 1205 (2015)
  10. Yamato T, Hideshima C, Prakash GKS, Olah GA, J. Org. Chem., 56(6), 2089 (1991)
  11. Yadav GD, Thorat TS, Kumbhar PS, Tetrahedron Lett., 34(3), 529 (1993)
  12. De La Cruz MHC, Da Silva JFC, Lachter ER, Appl. Catal. A: Gen., 245, 377 (2003)
  13. Kamalakar G, Komura K, Kubota Y, Sugi Y, J. Chem. Technol. Biotechnol., 81(6), 981 (2006)
  14. Mantri K, Komura K, Kubota Y, Sugi Y, J. Mol. Catal. A-Chem., 236, 168 (2005)
  15. Shimizu KI, Niimi K, Satsuma A, Appl. Catal. A: Gen., 349, 1 (2008)
  16. Podder S, Roy S, Tetrahedron, 63(37), 9146 (2007)
  17. Li BY, Leng KY, Zhang YM, Dynes JJ, Wang J, Hu YF, et al., J. Am. Chem. Soc., 137, 4243 (2015)
  18. Li J, Zhou Y, Mao D, Chen GJ, Wang XC, Yang XN, et al., Chem. Eng. J., 254, 54 (2014)
  19. Leng KY, Wang Y, Hou CM, Lancelot C, Lamonier C, Rives A, et al., J. Catal., 306, 100 (2013)
  20. Leng K, Sun S, Wang B, Sun L, Xu W, Sun Y, Catal. Commun., 28, 64 (2012)
  21. Khodaei MM, Nazari E, Tetrahedron Lett., 53(38), 5131 (2012)
  22. Kumar CR, Rao KTV, Prasad PSS, Lingaiah N, J. Mol. Catal. A-Chem., 337, 17 (2011)
  23. Zhang CY, Gao XQ, Zhang JH, Peng XJ, Chin. Chem. Lett., 20(8), 913 (2009)
  24. Prades A, Corberán R, Poyatos M, Peris E, Chemistry, 15(18), 4610 (2009)
  25. Sun YY, Prins R, Appl. Catal. A: Gen., 336, 11 (2008)
  26. Tuck CO, Pérez E, Horváth IT, Sheldon RA, Poliakoff M, Science, 337, 695 (2012)
  27. Thakur VK, Thakur MK, Raghavan P, Kessler MR, ACS Sustainable Chem. Eng., 2(5), 1072 (2014)
  28. Tenhaeff WE, Rios O, More K, Mcguire MA, Adv. Funct. Mater., 24, 86 (2014)
  29. Xie H, Zhao ZK, Wang Q, ChemSusChem, 5(5), 901 (2012)
  30. Chen DW, Liang FB, Feng DX, Du FL, Zhao G, Liu HZ, et al., Catal. Commun., 84, 159 (2016)
  31. Wu C, Chen W, Zhong L, Peng X, Sun R, Fang J, et al., J. Agric. Food Chem., 62(30), 7430 (2014)
  32. Tang H, Li N, Li G, Wang W, Wang A, Cong YU, et al., ACS Sustainable Chem. Eng., 6(4), 5645 (2018)
  33. Hu L, Tang X, Wu Z, Lin L, Xu JX, Xu N, et al., Chem. Eng. J., 263, 299 (2015)
  34. Bai CX, Zhu LF, Shen F, Qi XH, Bioresour. Technol., 220, 656 (2016)
  35. Konwar LJ, Samikannu A, Mäki-Arvela P, Boström D, Mikkola JP, Appl. Catal. B: Environ., 220, 314 (2018)
  36. Yu K, Kumar N, Aho A, Roine J, Heinmaa I, Murzin DY, et al., J. Catal., 335, 117 (2016)
  37. Cid R, Pecchi G, Appl. Catal., 14, 15 (1985)
  38. Wang JJ, Xu WJ, Ren JW, Liu XH, Lu GZ, Wang YQ, Green Chem., 13, 2678 (2011)
  39. Chen W, Peng XW, Zhong LX, Li Y, Sun RC, ACS Sustainable Chem. Eng., 3, 1366 (2015)
  40. Dong X, Jiang Y, Shan W, Zhang M, RSC Adv., 6(21), 17118 (2016)
  41. Suganuma S, Nakajima K, Kitano M, Yamaguchi D, Kato H, Hayashi S, et al., J. Am. Chem. Soc., 130(38), 12787 (2008)
  42. Lee D, Molecules, 18, 8168 (2013)
  43. Demir-Cakan R, Baccile N, Antonietti M, Titirici MM, Chem. Mater., 21(3), 484 (2009)
  44. Jesionowski T, Klapiszewski L, Milczarek G, Mater. Chem. Phys., 147(3), 1049 (2014)
  45. Li X, Jiang Y, Shuai LI, Wang L, Meng L, Mu X, J. Mater. Chem., 22(4), 1283 (2012)
  46. Yu X, Peng L, Gao X, He L, Chen K, RSC Adv., 8(28), 15762 (2018)
  47. Zhu J, Gan L, Li B, Yang X, Korean J. Chem. Eng., 34(1), 110 (2017)
  48. Nakajima K, Hara M, ACS Catal., 2, 1296 (2012)
  49. Kurnia I, Yoshida A, Chaihad N, Bayu A, Kasai Y, Abudula A, et al., Fuel Process. Technol., 196, 106175 (2019)
  50. Huang M, Luo J, Fang Z, Li H, Appl. Catal. B: Environ., 190, 103 (2016)
  51. Lu ET, Love SG, Nature, 438(7065), 177 (2005)
  52. Okamura M, Takagaki A, Toda M, Kondo JN, Domen K, Tatsumi T, et al., Chem. Mater., 18(13), 3039 (2006)
  53. Deng T, Li J, Yang Q, Yang Y, Lv G, Yao Y, et al., RSC Adv., 6(36), 30160 (2016)
  54. Liu WJ, Tian K, Jiang H, Yu HQ, Sci. Rep., 3, 2419 (2013)
  55. Chen T, Peng LC, Yu X, He L, Fuel, 219, 344 (2018)
  56. Mun SP, Cai Z, Zhang J, Mater. Lett., 100, 180 (2013)
  57. Ferrari AC, Robertson J, Phys. Rev. B, 61(20), 14095 (2000)
  58. Konwar LJ, Mäki-Arvela P, Salminen E, Kumar N, Thakur AJ, Mikkola JP, et al., Appl. Catal. B: Environ., 176-177, 20 (2015)
  59. Fraile JM, García-Bordejé E, Pires E, Roldán L, Carbon, 77, 1157 (2014)
  60. Hara M, Energy Environ. Sci., 3, 601 (2010)
  61. Zhu SY, Xu J, Cheng Z, Kuang YS, Wu Q, Wang B, et al., Appl. Catal. B: Environ., 268, 118732 (2020)
  62. Roberts AD, Li X, Zhang H, Carbon, 95, 268 (2015)
  63. Li XM, Lau SP, Tang LB, Ji RB, Yang PZ, Nanoscale, 6, 5323 (2014)
  64. Gan LH, Lyu L, Shen TR, Wang S, Appl. Catal. A: Gen., 574, 132 (2019)
  65. La Manna P, Soriente A, De Rosa M, Buonerba A, Talotta C, Gaeta C, et al., ChemSusChem, 12(8), 1673 (2019)
  66. Iqbal A, Tan KH, Shaari US, Ahmad NINB, Adam F, Lee HV, et al., J. Iran. Chem. Soc., 17, 1615 (2020)
  67. Nair DS, Kurian M, J. Saudi Chem. Soc., 23(2), 127 (2019)
  68. Fajar A, Nurdin F, Mukti R, Rasrendra C, Kadja G, Mater. Today Chem., 17, 100313 (2020)
  69. Khalil M, Kadja GTM, Ilmi MM, J. Ind. Eng. Chem., 93, 78 (2021)
  70. Maheswari R, Ramanathan A, Zhu HD , Araujo AAD, Chapman C, Tang Y, et al., J. Catal., 389, 657 (2020)
  71. Liu BY, Chen ZP, Huang JJ, Chen HY, Fang YX, Microporous Mesoporous Mater., 273, 235 (2019)
  72. Liu XY, Lu MH, Wang X, Lu JY, Yang JX, Catalysts, 9, 869 (2019)
  73. Nguyen VC, Bui NQ, Mascunan P, Vu TTH, Fongarland P, Essayem N, Appl. Catal. A: Gen., 552, 184 (2018)
  74. Tang XC, Niu SL, J. Ind. Eng. Chem., 69, 187 (2019)