Citation: LIU Ling-Tao, ZHANG Bin, LI Jing, MA Ding, KOU Yuan. Selective Degradation of Organosolv Lignin over Noble Metal Catalyst in a Two-Step Process[J]. Acta Physico-Chimica Sinica, ;2012, 28(10): 2343-2348. doi: 10.3866/PKU.WHXB201206152 shu

Selective Degradation of Organosolv Lignin over Noble Metal Catalyst in a Two-Step Process

1.
PKU Green Chemistry Center, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Received Date: 8 May 2012
Available Online: 15 June 2012
Fund Project: 国家重点基础研究发展规划项目(973) (2011CB201402)资助 (973) (2011CB201402)

Dioxane lignin, a typical organosolv lignin, was degraded by supported noble metal catalysts and phosphoric acid by a two-step method at different temperatures. The results showed that under 4 MPa H2 at 270 ℃ using Rh/C and 1% (w) phosphoric acid as catalysts, the highest total yield of the monomers and dimer was 16.9% after the first step, based on gas chromatography (GC) and gas chromatographymass spectrometry (GC-MS) analyses. Moreover, the raw products from the first step were analyzed by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), element analysis (EA), and gel permeation chromatography (GPC) to improve the understanding of the chemical transformations involved. The results indicated that the C－O－C bond linkages in the dioxane lignin were cleaved to form lower molecular-weight products, resulting in the degradation of lignin, and the carbonyl and carboxyl groups were partly removed. Oxygen content was reduced dramatically with increasing reaction temperature, from 35% (w) to 21% (w) after reacting at 270 ℃ for 10 h. Based on the analysis results, a reaction pathway for the degradation of lignin was proposed. Finally, the products from the first step could be hydrodeoxygenated to alkanes with carbon numbers in the range of gasoline and diesel with high selectivity catalyzed by Pd/C and phosphoric acid at 250 ℃.
- Dioxane lignin,
- Degradation,
- Hydrogenolysis,
- Hydrodeoxygenation,
- Liquid fuel
1. [1]
  
  (1) Huber, G.W.; Iborra, S.; Corma, A. Chem. Rev. 2006, 106, 4044.doi: 10.1021/cr068360d
2. [2]
  (2) Huber, G.W.; Chheda, J. N.; Barrett, C. J.; Dumesic, J. A.Science 2005, 308, 1446.
3. [3]
  (3) Rinaldi, R.; Palkovits, R.; Schueth, F. Angew. Chem. Int. Edit.2008, 47, 8047. doi: 10.1002/anie.200802879
4. [4]
  (4) Deng, L.; Li, J.; Lai, D. M.; Fu, Y.; Guo, Q. X. Angew. Chem. Int. Edit. 2009, 48, 6529. doi: 10.1002/anie.200902281
5. [5]
  (5) Bond, J. Q.; Alonso, D. M.;Wang, D.;West, R. M.; Dumesic, J.A. Science 2010, 327, 1110. doi: 10.1126/science.1184362
6. [6]
  (6) Bozell, J. J. Science 2010, 329, 522. doi: 10.1126/science.1191662
7. [7]
  (7) Geilen, F. M. A.; Engendahl, B.; Harwardt, A.; Marquardt,W.;Klankermayer, J.; Leitner,W. Angew. Chem. Int. Edit. 2010, 49,5510. doi: 10.1002/anie.201002060
8. [8]
  (8) Corma, A.; de la Torre, O.; Renz, M.; Villandier, N. Angew. Chem. Int. Edit. 2011, 50, 2375.
9. [9]
  (9) Du, X. L.; He, L.; Zhao, S.; Liu, Y. M.; Cao, Y.; He, H. Y.; Fan,K. N. Angew. Chem. Int. Edit. 2011, 50, 7815. doi: 10.1002/anie.201100102
10. [10]
  (10) Rackemann, D.W.; Doherty,W. O. S. Biofuel. Bioprod. Bior.2011, 5, 198. doi: 10.1002/bbb.267
11. [11]
  (11) Fukuoka, A.; Dhepe, P. L. Angew. Chem. Int. Edit. 2006, 45,5161. doi: 10.1002/anie.200601921
12. [12]
  (12) Luo, C.;Wang, S.; Liu, H. Angew. Chem. Int. Edit. 2007, 46,7636. doi: 10.1002/anie.200702661
13. [13]
  (13) Ji, N.; Zhang, T.; Zheng, M.;Wang, A.;Wang, H.;Wang, X.;Chen, J. G. Angew. Chem. Int. Edit. 2008, 47, 8510. doi: 10.1002/anie.200803233
14. [14]
  (14) Zhao, H.; Holladay, J. E.; Brown, H.; Zhang, Z. C. Science2007, 316, 1597. doi: 10.1126/science.1141199
15. [15]
  (15) Binder, J. B.; Raines, R. T. J. Am. Chem. Soc. 2009, 131, 1979.doi: 10.1021/ja808537j
16. [16]
  (16) Zhang, Z.; Zhao, Z. K. Bioresource Technol. 2010, 101, 1111.doi: 10.1016/j.biortech.2009.09.010
17. [17]
  (17) Mascal, M.; Nikitin, E. B. Angew. Chem. Int. Edit. 2008, 47,7924. doi: 10.1002/anie.200801594
18. [18]
  (18) Hu, S.; Zhang, Z.; Song, J.; Zhou, Y.; Han, B. Green Chem.2009, 11, 1746. doi: 10.1039/b914601f
19. [19]
  (19) Yan, N.; Zhao, C.; Gan,W. J.; Kou, Y. Chin. J. Catal. 2006, 27,1159. [颜宁, 赵晨, 甘维佳, 寇元. 催化学报, 2006, 27,1159.]
20. [20]
  (20) Yan, N.; Zhao, C.; Luo, C.; Dyson, P. J.; Liu, H.; Kou, Y. J. Am. Chem. Soc. 2006, 128, 8714. doi: 10.1021/ja062468t
21. [21]
  (21) Pepper, J. M.; Rahman, M. D. Cell. Chem. Technol. 1987, 21,233.
22. [22]
  (22) Thring, R.W.; Katikaneni, S. P. R.; Bakhshi, N. N. Fuel Process. Technol. 2000, 62, 17. doi: 10.1016/S0378-3820(99)00061-2
23. [23]
  (23) Jackson, M. A.; Compton, D. L.; Boateng, A. A. J. Anal. Appl. Pyrol. 2009, 85, 226. doi: 10.1016/j.jaap.2008.09.016
24. [24]
  (24) Stark, K.; Taccardi, N.; Bosmann, A.;Wasserscheid, P.ChemSusChem 2010, 3, 719. doi: 10.1002/cssc.200900242
25. [25]
  (25) Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.;Weckhuysen,B. M. Chem. Rev. 2010, 110, 3552. doi: 10.1021/cr900354u
26. [26]
  (26) Yan, N.; Zhao, C.; Dyson, P. J.;Wang, C.; Liu, L. T.; Kou, Y.ChemSusChem 2008, 1, 626. doi: 10.1002/cssc.200800080
27. [27]
  (27) Zhao, C.; Kou, Y.; Lemonidou, A. A.; Li, X.; Lercher, J. A.Angew. Chem. Int. Edit. 2009, 48, 3987. doi: 10.1002/anie.200900404
28. [28]
  (28) Zhao, C.; Kou, Y.; Lemonidou, A. A.; Li, X.; Lercher, J. A.Chem. Commun. 2010, 46, 412.
29. [29]
  (29) Zhao, C.; He, J.; Lemonidou, A. A.; Li, X.; Lercher, J. A.J. Catal. 2011, 280, 8. doi: 10.1016/j.jcat.2011.02.001
30. [30]
  (30) Yan, N.; Yuan, Y.; Dykeman, R.; Kou, Y.; Dyson, P. J. Angew. Chem. Int. Edit. 2010, 49, 5549. doi: 10.1002/anie.201001531
31. [31]
  (31) Pepper, J. M.; Siddiqueullah, M. Can. J. Chem. 1961, 39, 1454.doi: 10.1139/v61-185
32. [32]
  (32) Derkacheva, O.; Sukhov, D. Macromol. Symp. 2008, 265, 61.doi: 10.1002/masy.200850507
33. [33]
  (33) He, J. X.; Zhang,W.; Li, K. J.; Cui, S. Z.;Wang, S. Y. J. Text. Res. 2009, 30, 13. [何建新, 章伟, 李克兢, 崔世忠, 王善元.纺织学报, 2009, 30, 13.]
34. [34]
  (34) Jung, H. J. G.; Himmelsbach, D. S. J. Agric. Food Chem. 1989,81.
35. [35]
  (35) Zhang, A. P.; Liu, C. F.; Sun, R. C. Ind. Crop. Prod. 2010, 31,357. doi: 10.1016/j.indcrop.2009.12.003
36. [36]
  (36) Faix, O. Holzforschung 1991, 45 (Suppl.), 21.
37. [37]
  (37) Dorris, G. M.; Gray, D. G. Cell. Chem. Technol. 1978, 12, 9.
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