Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes

doi:10.1016/S1872-2067(24)60186-5

Chinese Journal of Catalysis ›› 2025, Vol. 68: 356-365.DOI: 10.1016/S1872-2067(24)60186-5

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Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes

Lin Dong^a^,^b^,^c, Zhiqiang Fang^b, Qianbo Yuan^a, Yong Fan^a, Yong Yang^d, Ping Wang^d, Shixiong Sheng^d^,^*(), Yanqin Wang^e^,^*(), Zupeng Chen^a^,^d^,^*()

^aJiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
^bState Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
^cFeili Chemical Engineering (Zhejiang Suichang) Co. Ltd., Suichang 323316, Zhejiang, China
^dDehua TB New Decoration Material Co., Ltd, Huzhou 313200, Zhejiang, China
^eKey Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2024-08-30 Accepted:2024-10-22 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: 38701@qq.com (S. Sheng), wangyanqin@ecust.edu.cn (Y. Wang), czp@njfu.edu.cn (Z. Chen).
Supported by:
National Key Research and Development Program of China(2023YFD2200505);National Natural Science Foundation of China(22202105);National Natural Science Foundation of China(22002043);Natural Science Foundation of Jiangsu Higher Education Institutions of China(21KJA150003);Innovation and Entrepreneurship Team Program of Jiangsu Province(JSSCTD202345);China Postdoctoral Science Foundation(2023M731703);China Postdoctoral Science Foundation(2024T170415);State Key Laboratory of Pulp and Paper Engineering(202414)

Abstract

Abstract:

Many strategies have been proposed to produce arenes from lignin as liquid fuel additives. However, the development of these methods is limited by the low yield of products, low atom utilization, and inefficient lignin depolymerization. Herein, we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%. Particularly, high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin. The process begins with the reductive depolymerization of formaldehyde-stabilized lignin, followed by transmethylation between lignin monomers over Au/Nb₂O₅ catalyst, and the Ru/Nb₂O₅-catalyzed hydrodeoxygenation. This work demonstrates the potential of value-added arenes production directly from lignin.

Key words: Lignin, Arene, Transmethylation, Hydrodeoxygenation, Liquid fuel additive

Lin Dong, Zhiqiang Fang, Qianbo Yuan, Yong Fan, Yong Yang, Ping Wang, Shixiong Sheng, Yanqin Wang, Zupeng Chen. Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes[J]. Chinese Journal of Catalysis, 2025, 68: 356-365.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60186-5

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Figures/Tables 7

Scheme 1. Strategies employed for arenes production from lignin. (a) The traditional route for arenes production from lignin. (b) The proposed route for high-carbon-number arenes production from lignin in this work.

Fig. 1. Production of lignin monomers from birch wood under different reaction conditions. Extraction conditions: birch wood 1.0 g, dioxane 10 mL, stabilizing agent 0-1.5 mL, HCl solution 420 μL, 80 °C, 5 h; Hydrogenolysis conditions: lignin 0.2 g, catalyst 0.1 g, dioxane 20 mL, H2 4.0 MPa, 250 °C, 15 h. The extracted lignin yield was calculated based on the mass of the wood.

Fig. 2. Production of lignin monomers from different types of wood. Extraction conditions: wood 1.0 g, dioxane 10 mL, formaldehyde 1.5 mL, HCl solution 420 μL, 80 °C, 5 h; Hydrogenolysis conditions: lignin 0.2 g, 5% Ni/C 0.1 g, dioxane 20 mL, H2 4.0 MPa, 250 °C, 15 h. The extracted lignin yield was calculated based on the mass of the wood.

Fig. 3. Reaction results for the transmethylation of 2-methoxy-4-propylphenol in a batch reactor under different reaction conditions. Reaction conditions: 2-methoxy-4-propylphenol 0.5 g, catalyst 0.2 g, solvent 15 mL, H2 5.0 MPa, 300 °C, 10 h.

Fig. 4. Reaction results for the transmethylation of 2,6-dimethoxy-4-propylphenol, 2,6-dimethoxy-4-ethylphenol, and 2-methoxy-5-methyl-4-propylphenol in a batch reactor. Reaction conditions: substrate 0.5 g, Au/Nb2O5 0.2 g, dioxane 15 mL, H2 pressure 5.0 MPa, 300 °C, 10 h.

Fig. 5. Reaction results for the hydrodeoxygenation of 2-methyl-4-propylphenol for different catalysts in a batch reactor. Reaction conditions: 2-methyl-4-propylphenol 0.2 g, catalyst 0.1 g, H2O 15 mL, H2 0.5 MPa, 250 °C, 5 h.

Table 1 Results of conversion of various wood into arenes.

References

[1]	L. R. Lynd, G. T. Beckham, A. M. Guss, L. N. Jayakody, E. M. Karp, C. Maranas, R. L. McCormick, D. Amador-Noguez, Y. J. Bomble, B. H. Davison, C. Foster, M. E. Himmel, E. K. Holwerda, M. S. Laser, C. Y. Ng, D. G. Olson, Y. Román-Leshkov, C. T. Trinh, G. A. Tuskan, V. Upadhayay, D. R. Vardon, L. Wang, C. E. Wyman, Energy Environ. Sci., 2022, 15, 938-990.
[2]	M. A. Peters, C. T. Alves, J. A. Onwudili, Energies, 2023, 16, 6100.
[3]	P. Lahijani, M. Mohammadi, A. R. Mohamed, F. Ismail, K. T. Lee, G. Amini, Energy Conv. Manag., 2022, 268, 115956.
[4]	M. Shahabuddin, M. T. Alam, B. B. Krishna, T. Bhaskar, G. Perkins, Bioresour. Technol., 2020, 312, 123596.
[5]	Y. H. Luo, R. Zhang, Y. T. He, D. F. Lou, R. Zhu, C. Zhu, M. H. Fan, Q. X. Li, Bioresour. Technol., 2023, 382, 129175.
[6]	X. S. Zhang, H. W. Lei, L. Zhu, M. Qian, J. C. Chan, X. L. Zhu, Y. P. Liu, G. Yadavalli, D. Yan, L. Wang, Q. Bu, Y. Wei, J. Wu, S. L. Chen, Catal. Sci. Technol., 2016, 6, 4210-4220.
[7]	X. Zhang, L. Pan, L. Wang, J. Zou, Chem. Eng. Sci., 2018, 180, 95-125.
[8]	H. Tang, Y. Hu, G. Li, A. Wang, G. L. Xu, C. Yu, X. D. Wang, T. Zhang, N. Li, Green Chem., 2019, 21, 3789-3795.
[9]	H. Tang, N. Li, G. Li, A. Wang, Y. Cong, G. Xu, X. Wang, T. Zhang, Green Chem., 2019, 21, 2709-2719.
[10]	G. Li, R. Wang, J. Pang, A. Wang, N. Li, T. Zhang, Chem. Rev., 2024, 124, 2889-2954.
[11]	F. Cheng, C. E. Brewer, Renewable Sustainable Energy Rev. 2017, 72, 673-722.
[12]	C. Zhang, X. Shen, Y. Jin, J. Cheng, C. Cai, F. Wang, Chem. Rev., 2023, 123, 4510-4601.
[13]	S. S. Wong, R. Shu, J. Zhang, H. Liu, N. Yan, Chem. Soc. Rev., 2020, 49, 5510-5560.
[14]	W. Schutyser, T. Renders, S. Van den Bosch, S. F. Koelewijn, G. T. Beckham, B. F. Sels, Chem. Soc. Rev., 2018, 47, 852-908.
[15]	C. Li, X. Zhao, A. Wang, G. W. Huber, T. Zhang, Chem. Rev., 2015, 115, 11559-11624.
[16]	Z. H. Sun, B. Fridrich, A. de Santi, S. Elangovan, K. Barta, Chem. Rev., 2018, 118, 614-678.
[17]	Y. Jing, L. Dong, Y. Guo, X. Liu, Y. Wang, ChemSusChem, 2020, 13, 4181-4198.
[18]	X. J. Shen, C. F. Zhang, B. X. Han, F. Wang, Chem. Soc. Rev., 2022, 51, 1608-1628.
[19]	Z. Zhang, J. Song, B. Han, Chem. Rev., 2017, 117, 6834-6880.
[20]	Y. Jing, Y. Guo, Q. Xia, X. Liu, Y. Wang, Chem, 2019, 5, 2520-2546.
[21]	R. Shen, L. Tao, B. Yang, Biofuels Bioprod. Biorefining, 2019, 13, 486-501.
[22]	Y. Shao, Q. Xia, L. Dong, X. Liu, X. Han, S. F. Parker, Y. Cheng, L. L. Daemen, A. J. Ramirez-Cuesta, S. Yang, Y. Wang, Nat. Commun., 2017, 8, 16104.
[23]	Z. Luo, Z. Zheng, Y. C. Wang, G. Sun, H. Jiang, C. Zhao, Green Chem., 2016, 18, 5845-5858.
[24]	L. Dong, L. Lin, X. Han, X. Q. Si, X. H. Liu, Y. Guo, F. Lu, S. Rudic, S. F. Parker, S. H. Yang, Y. Q. Wang, Chem, 2019, 5, 1521-1536.
[25]	Y. Xin, L. Dong, Y. Guo, X. Liu, Y. Hu, Y. Wang, J. Catal., 2019, 375, 202-212.
[26]	L. Shuai, M. T. Amiri, Y. M. Questell-Santiago, F. Héroguel, Y. Li, H. Kim, R. Meilan, C. Chapple, J. Ralph, J. S. Luterbacher, Science, 2016, 354, 329-333.
[27]	W. Lan, M. T. Amiri, C. M. Hunston, J. S. Luterbacher, Angew. Chem. Int. Ed., 2018, 57, 1356-1360.
[28]	S. V. den Bosch, W. Schutyser, S.-F. Koelewijin, T. Renders, C. M. Courtin, B. F. Sels, Chem. Commun., 2015, 51, 13158-13161.
[29]	Q. Song, F. Wang, J. Cai, Y. Wang, J. Zhang, W. Yu, J. Xu, Energy Environ. Sci., 2013, 6, 994-1007.
[30]	I. Klein, B. Saha, M. M. Abu-Omar, Catal. Sci. Technol., 2015, 5, 3242-3245.
[31]	L. Dong, Y. Xin, X. Liu, Y. Guo, C.-W. Pao, J.-L. Chen, Y. Wang, Green Chem., 2019, 21, 3081-3090.
[32]	J. Mao, J. Zhou, Z. Xia, Z. G. Wang, Z. Xu, W. Xu, P. Yan, K. Liu, X. Guo, Z. C. Zhang, ACS Catal., 2017, 7, 695-705.
[33]	X. Huang, J. M. Ludenhoff, M. Dirks, X. Ouyang, M. D. Boot, E. J. M. Hensen, ACS Catal., 2018, 8, 11184-11190.
[34]	T. Ghampson, R. Canales, N. Escalona, Appl. Catal. A, 2018, 549, 225-236.
[35]	L. Dong, Y. Shao, X. Han, X. Liu, Q. Xia, S. F. Park, Y. Cheng, L. L. Daemen, A. J. Ramirez-Cuesta, Y. Wang, S. Yang, Catal. Sci. Technol., 2018, 8, 6129-6136.

Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes

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