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.
1. [1]
  Fei ZHOU , Xiaolin JIA . Co₃O₄/TiO₂ composite photocatalyst: Preparation and synergistic degradation performance of toluene. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2232-2240. doi: 10.11862/CJIC.20240236
2. [2]
  Yadan Luo , Hao Zheng , Xin Li , Fengmin Li , Hua Tang , Xilin She . 调节O,S共掺杂C₃N₄中的活性氧生成以促进光催化降解微塑料. Acta Physico-Chimica Sinica, 2025, 41(6): 100052-. doi: 10.1016/j.actphy.2025.100052
3. [3]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
4. [4]
  Jiahui YU , Jixian DONG , Yutong ZHAO , Fuping ZHAO , Bo GE , Xipeng PU , Dafeng ZHANG . The morphology control and full-spectrum photodegradation tetracycline performance of microwave-hydrothermal synthesized BiVO₄:Yb³⁺,Er³⁺ photocatalyst. Journal of Fuel Chemistry and Technology, 2025, 53(3): 348-359. doi: 10.1016/S1872-5813(24)60514-1
5. [5]
  Jinwang Wu , Qijing Xie , Chengliang Zhang , Haifeng Shi . 自旋极化增强ZnFe_1.2Co_0.8O₄/BiVO₄ S型异质结光催化性能降解四环素. Acta Physico-Chimica Sinica, 2025, 41(5): 100050-. doi: 10.1016/j.actphy.2025.100050
6. [6]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . 碳基催化剂催化有机液体氢载体脱氢研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-. doi: 10.1016/j.actphy.2024.100044
7. [7]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . 软模板法诱导Cu/Al₂O₃深孔道结构促进等离子催化CO₂加氢制二甲醚. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054
8. [8]
  Zizheng LU , Wanyi SU , Qin SHI , Honghui PAN , Chuanqi ZHAO , Chengfeng HUANG , Jinguo PENG . Surface state behavior of W doped BiVO₄ photoanode for ciprofloxacin degradation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 591-600. doi: 10.11862/CJIC.20230225
9. [9]
  Lijun Zhou , Dongmei Wang , Jiameng Wang , Tongjie Yao , Mei Qi , Yin Kong , Yan Song . Teaching Case Design of “Degradation and Aging” as an Ideological and Political Demonstration Course. University Chemistry, 2025, 40(4): 80-86. doi: 10.12461/PKU.DXHX202405113
10. [10]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
11. [11]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
12. [12]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
13. [13]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
14. [14]
  Yujia LI , Tianyu WANG , Fuxue WANG , Chongchen WANG . Direct Z-scheme MIL-100(Fe)/BiOBr heterojunctions: Construction and photo-Fenton degradation for sulfamethoxazole. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 481-495. doi: 10.11862/CJIC.20230314
15. [15]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
16. [16]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-Scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-. doi: 10.3866/PKU.WHXB202403005
17. [17]
  Hongbo Zhang , Yihong Tang , Suxia Zhang , Yuanting Li . Electrochemical Monitoring of Photocatalytic Degradation of Phenol Pollutants: A Recommended Comprehensive Analytical Chemistry Experiment. University Chemistry, 2024, 39(6): 326-333. doi: 10.3866/PKU.DXHX202310013
18. [18]
  Lijuan Liu , Xionglei Wang . Preparation of Hydrogels from Waste Thermosetting Unsaturated Polyester Resin by Controllable Catalytic Degradation: A Comprehensive Chemical Experiment. University Chemistry, 2024, 39(11): 313-318. doi: 10.12461/PKU.DXHX202403060
19. [19]
  Yingqi BAI , Hua ZHAO , Huipeng LI , Xinran REN , Jun LI . Perovskite LaCoO₃/g-C₃N₄ heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 480-490. doi: 10.11862/CJIC.20240259
20. [20]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029

Get Citation

PDF

XML

Metrics

PDF Downloads(810)
Abstract views(2399)
HTML views(43)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142