Insights into depolymerization pathways and mechanism of alkali lignin over a Ni1.2–ZrO2/WO3/γ-Al2O3 catalyst

doi:10.1016/j.cjche.2021.07.018

中国化学工程学报 ›› 2022, Vol. 48 ›› Issue (8): 191-201.DOI: 10.1016/j.cjche.2021.07.018

Insights into depolymerization pathways and mechanism of alkali lignin over a Ni_1.2–ZrO₂/WO₃/γ-Al₂O₃ catalyst

Xinyu Lu¹, Dandan Wang¹, Haoquan Guo¹, Pengcheng Xiu¹, Jiajia Chen¹, Yu Qin¹, Hossain Mahmud Robin¹, Chaozhong Xu¹, Xingguang Zhang², Xiaoli Gu¹

1. Co–Innovation Center for Efficient Processing and Utilization of Forest Products, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;
2. Department of Chemistry, School of Science, University of Shanghai for Science and Technology, Shanghai 200093, China

收稿日期:2021-04-28 修回日期:2021-07-18 出版日期:2022-08-28 发布日期:2022-09-30
通讯作者: Xingguang Zhang,E-mail:x.g.zhang@usst.edu.cn;Xiaoli Gu,E-mail:guxiaoli@njfu.edu.cn
基金资助:
This research was financially supported by the National Natural Science Foundation of China ( 21774059), the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions.

Insights into depolymerization pathways and mechanism of alkali lignin over a Ni_1.2–ZrO₂/WO₃/γ-Al₂O₃ catalyst

Xinyu Lu¹, Dandan Wang¹, Haoquan Guo¹, Pengcheng Xiu¹, Jiajia Chen¹, Yu Qin¹, Hossain Mahmud Robin¹, Chaozhong Xu¹, Xingguang Zhang², Xiaoli Gu¹

1. Co–Innovation Center for Efficient Processing and Utilization of Forest Products, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;
2. Department of Chemistry, School of Science, University of Shanghai for Science and Technology, Shanghai 200093, China

Received:2021-04-28 Revised:2021-07-18 Online:2022-08-28 Published:2022-09-30
Contact: Xingguang Zhang,E-mail:x.g.zhang@usst.edu.cn;Xiaoli Gu,E-mail:guxiaoli@njfu.edu.cn
Supported by:
This research was financially supported by the National Natural Science Foundation of China ( 21774059), the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions.

摘要/Abstract

摘要： This study performed catalytic depolymerization of alkali lignin over Ni-based catalysts. Effects of different promoters (Zr and W), Ni loadings, reaction temperatures, and the addition of formic acid and catalyst on lignin conversion and products distribution were all investigated. The result showed that the highest oil yield (40.1% (mass)) was obtained at 240?℃ over Ni_1.2/γ-Al₂O₃ promoted by Zr and W species. Quantitative analysis indicates that Zr and W species prefer to lignin depolymerization while Ni active phase prefer to hydrodeoxygenation and hydrogenation. The interconversion of products derived from lignin depolymerization was determined by gas chromatography-mass spectrometer, which demonstrated that phenolic compounds were dominant products in all lignin derived bio-oils, wherein the proportion of vanillin was highest (65.7%) at 180?℃, while that of alkyl guaiacols increased with the increase of temperature (from 12.45% at 180?℃ to 66.67% at 240?℃). Residual lignin obtained after lignin depolymerization was also investigated for detecting differences on functional groups, wherein the disappearing peaks at 1511?cm^?1 (stretching of aromatic rings), 1267, 1215 and 1035?cm^?1 (vibrations of guaiacyl and syringyl units) were detected by Fourier transform infrared spectrometry. Additionally, the higher O/C ratio measured by elemental analysis also confirmed that alkali lignin was depolymerized effectively under mild conditions.

关键词: Alkali lignin, Formic acid, Chemical reduction, Phenolic compounds

Abstract: This study performed catalytic depolymerization of alkali lignin over Ni-based catalysts. Effects of different promoters (Zr and W), Ni loadings, reaction temperatures, and the addition of formic acid and catalyst on lignin conversion and products distribution were all investigated. The result showed that the highest oil yield (40.1% (mass)) was obtained at 240?℃ over Ni_1.2/γ-Al₂O₃ promoted by Zr and W species. Quantitative analysis indicates that Zr and W species prefer to lignin depolymerization while Ni active phase prefer to hydrodeoxygenation and hydrogenation. The interconversion of products derived from lignin depolymerization was determined by gas chromatography-mass spectrometer, which demonstrated that phenolic compounds were dominant products in all lignin derived bio-oils, wherein the proportion of vanillin was highest (65.7%) at 180?℃, while that of alkyl guaiacols increased with the increase of temperature (from 12.45% at 180?℃ to 66.67% at 240?℃). Residual lignin obtained after lignin depolymerization was also investigated for detecting differences on functional groups, wherein the disappearing peaks at 1511?cm^?1 (stretching of aromatic rings), 1267, 1215 and 1035?cm^?1 (vibrations of guaiacyl and syringyl units) were detected by Fourier transform infrared spectrometry. Additionally, the higher O/C ratio measured by elemental analysis also confirmed that alkali lignin was depolymerized effectively under mild conditions.

Key words: Alkali lignin, Formic acid, Chemical reduction, Phenolic compounds

Xinyu Lu, Dandan Wang, Haoquan Guo, Pengcheng Xiu, Jiajia Chen, Yu Qin, Hossain Mahmud Robin, Chaozhong Xu, Xingguang Zhang, Xiaoli Gu. Insights into depolymerization pathways and mechanism of alkali lignin over a Ni_1.2–ZrO₂/WO₃/γ-Al₂O₃ catalyst[J]. 中国化学工程学报, 2022, 48(8): 191-201.

参考文献

[1] V. Mendu, T. Shearin, J.E. Campbell, Jr., J. Stork, J. Jae, M. Crocker, G. Huber, S. DeBolt, Global bioenergy potential from high-lignin agricultural residue, Proc. Natl. Acad. Sci. USA. 109 (10) (2012) 4014–4019
[2] W.M. Budzianowski, K. Postawa, Total Chain Integration of sustainable biorefinery systems, Appl. Energy 184 (2016) 1432–1446
[3] D. Bbosa, M. Mba-Wright, R.C. Brown, More than ethanol: A techno-economic analysis of a corn stover-ethanol biorefinery integrated with a hydrothermal liquefaction process to convert lignin into biochemicals, Biofuel. Bioprod. Bioref. 12 (3) (2018) 497–509
[4] L. Shuai, M.T. Amiri, Y.M. Questell-Santiago, F. Héroguel, Y.D. Li, H. Kim, R. Meilan, C. Chapple, J. Ralph, J.S. Luterbacher, Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization, Science 354 (6310) (2016) 329–333
[5] C.Z. Li, X.C. Zhao, A.Q. Wang, G.W. Huber, T. Zhang, Catalytic transformation of lignin for the production of chemicals and fuels, Chem. Rev. 115 (21) (2015) 11559–11624
[6] J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, B.M. Weckhuysen, The catalytic valorization of lignin for the production of renewable chemicals, Chem. Rev. 110 (6) (2010) 3552–3599
[7] P. Azadi, O.R. Inderwildi, R. Farnood, D.A. King, Liquid fuels, hydrogen and chemicals from lignin: A critical review, Renew. Sustain. Energy Rev. 21 (2013) 506–523
[8] J.M. Ha, K.R. Hwang, Y.M. Kim, J. Jae, K.H. Kim, H.W. Lee, J.Y. Kim, Y.K. Park, Recent progress in the thermal and catalytic conversion of lignin, Renew. Sustain. Energy Rev. 111 (2019) 422–441
[9] H. Wang, H. Ruan, H. Pei, H. Wang, X. Chen, M.P. Tucker, J.R. Cort, B. Yang, Biomass-derived lignin to jet fuel range hydrocarbons via aqueous phase hydrodeoxygenation, Green Chem. 17 (2015) 5131–5135
[10] J. Hu, S.H. Zhang, R. Xiao, X.X. Jiang, Y.J. Wang, Y.H. Sun, P. Lu, Catalytic transfer hydrogenolysis of lignin into monophenols over platinum–rhenium supported on titanium dioxide using isopropanol as in situ hydrogen source, Bioresour. Technol. 279 (2019) 228–233
[11] L.P. Kong, L.L. Zhang, J.L. Gu, L. Gou, L.F. Xie, Y.Y. Wang, L.Y. Dai, Catalytic hydrotreatment of kraft lignin into aromatic alcohols over nickel–rhenium supported on niobium oxide catalyst, Bioresour. Technol. 299 (2020)122582
[12] H.W. Lee, Y.M. Kim, J. Jae, B.H. Sung, S.C. Jung, S.C. Kim, J.K. Jeon, Y.K. Park, Catalytic pyrolysis of lignin using a two-stage fixed bed reactor comprised of in-situ natural zeolite and ex-situ HZSM-5, J. Anal. Appl. Pyrolysis 122 (2016) 282–288
[13] N. Mahmood, Z. Yuan, J. Schmidt, C. Xu, Production of polyols via direct hydrolysis of kraft lignin: Effect of process parameters, Bioresour. Technol. 139 (2013) 13–20
[14] J.D.P. Araújo, C.A. Grande, A.E. Rodrigues, Vanillin production from lignin oxidation in a batch reactor, Chem. Eng. Res. Des. 88 (8) (2010) 1024–1032
[15] A. Rahimi, A. Ulbrich, J.J. Coon, S.S. Stahl, Formic-acid-induced depolymerization of oxidized lignin to aromatics, Nature 515 (7526) (2014) 249–252
[16] J.H. Dai, A.F. Patti, K. Saito, Recent developments in chemical degradation of lignin: Catalytic oxidation and ionic liquids, Tetrahedron Lett. 57 (45) (2016) 4945–4951
[17] M.P. Pandey, C.S. Kim, Lignin depolymerization and conversion: A review of thermochemical methods, Chem. Eng. Technol. 34 (1) (2011) 29–41
[18] J.G. Zhang, H. Asakura, J. van Rijn, J. Yang, P. Duchesne, B. Zhang, X. Chen, P. Zhang, M. Saeys, N. Yan, Highly efficient, NiAu-catalyzed hydrogenolysis of lignin into phenolic chemicals, Green Chem. 16 (5) (2014) 2432–2437
[19] H. Konnerth, J.G. Zhang, D. Ma, M.H.G. Prechtl, N. Yan, Base promoted hydrogenolysis of lignin model compounds and organosolv lignin over metal catalysts in water, Chem. Eng. Sci. 123 (2015) 155–163
[20] M.O. Bengoechea, N. Miletíc, M.H. Vogt, P.L. Arias, T. Barth, Analysis of the effect of temperature and reaction time on yields, compositions and oil quality in catalytic and non-catalytic lignin solvolysis in a formic acid/water media using experimental design, Bioresour. Technol. 234 (2017) 86–98
[21] I. Kristianto, S.O. Limarta, H. Lee, J.M. Ha, D.J. Suh, J. Jae, Effective depolymerization of concentrated acid hydrolysis lignin using a carbon-supported ruthenium catalyst in ethanol/formic acid media, Bioresour. Technol. 234 (2017) 424–431
[22] H.W. Guo, D.M. Miles–Barrett, B. Zhang, A.Q. Wang, T. Zhang, N.J. Westwood, C.Z. Li, Is oxidation–reduction a real robust strategy for lignin conversion? A comparative study on lignin and model compounds, Green Chem. 21 (4) (2019) 803–811
[23] W.Y. Xu, S.J. Miller, P.K. Agrawal, C.W. Jones, Depolymerization and hydrodeoxygenation of switchgrass lignin with formic acid, ChemSusChem 5 (4) (2012) 667–675
[24] S.M. Zhang, L. Su, L. Liu, G.Z. Fang, Degradation on hydrogenolysis of soda lignin using CuO/SO42–/ZrO2 as catalyst, Ind. Crop. Prod. 77 (2015) 451–457
[25] L.P. Kong, C.Z. Liu, J. Gao, Y.Y. Wang, L.Y. Dai, Efficient and controllable alcoholysis of Kraft lignin catalyzed by porous zeolite-supported nickel–copper catalyst, Bioresour. Technol. 276 (2019) 310–317
[26] D. Wang, G.C. Li, C.H. Zhang, Z. Wang, X.B. Li, Nickel nanoparticles inlaid in lignin-derived carbon as high effective catalyst for lignin depolymerization, Bioresour. Technol. 289 (2019)121629
[27] Y.D. Bi, X.J. Lei, G.H. Xu, H. Chen, J.L. Hu, Catalytic fast pyrolysis of kraft lignin over hierarchical HZSM-5 and Hβzeolites, Catalysts 8 (2) (2018)82
[28] W.X. Guan, X. Chen, S.H. Jin, C.H. Li, C.W. Tsang, C. Liang, Highly stable Nb2O5–Al2O3 composites supported Pt catalysts for hydrodeoxygenation of diphenyl ether, Ind. Eng. Chem. Res. 56 (47) (2017) 14034–14042
[29] Q. Lu, Z.B. Zhang, X.Q. Wang, C.Q. Dong, Y.Q. Liu, Catalytic upgrading of biomass fast pyrolysis vapors using ordered mesoporous ZrO2, TiO2 and SiO2, Energy Procedia 61 (2014) 1937–1941
[30] H.W. Guo, Z.J. Qi, Y.X. Liu, H.A. Xia, L. Li, Q.T. Huang, A.Q. Wang, C.Z. Li, Tungsten-based catalysts for lignin depolymerization: The role of tungsten species in C–O bond cleavage, Catal. Sci. Technol. 9 (9) (2019) 2144–2151
[31] W.Y. Wang, K. Wu, P.L. Liu, L. Li, Y.Q. Yang, Y. Wang, Hydrodeoxygenation of p-cesol over Pt/Al2O3 catalyst promoted by ZrO2, CeO2, and CeO2–ZrO2, Ind. Eng. Chem. Res. 55 (28) (2016) 7598–7603
[32] Y.K. Hong, D.W. Lee, H.J. Eom, K.Y. Lee, The catalytic activity of Pd/WOx/γ-Al2O3 for hydrodeoxygenation of guaiacol, Appl. Catal. B: Environ. 150–151 (2014) 438–445
[33] A. Ramesh, P. Tamizhdurai, V.L. Mangesh, K. Palanichamy, S. Gopinath, K. Sureshkumar, K. Shanthi, Mg/SiO2–Al2O3 supported nickel catalysts for the production of naphthenic hydrocarbon fuel by hydro-de-oxygenation of eugenol, Int. J. Hydrog. Energy 44 (47) (2019) 25607–25620
[34] D.P. Phan, T.K. Vo, V.N. Le, J. Kim, E.Y. Lee, Spray pyrolysis synthesis of bimetallic NiMo/Al2O3–TiO2 catalyst for hydrodeoxygenation of guaiacol: Effects of bimetallic composition and reduction temperature, J. Ind. Eng. Chem. 83 (2020) 351–358
[35] A. Bjeli?, B. Likozar, M. Grilc, Scaling of lignin monomer hydrogenation, hydrodeoxygenation and hydrocracking reaction micro-kinetics over solid metal/acid catalysts to aromatic oligomers, Chem. Eng. J. 399 (2020) 125712
[36] D. Singh, P.L. Dhepe, Understanding the influence of alumina supported ruthenium catalysts synthesis and reaction parameters on the hydrodeoxygenation of lignin derived monomers, Mol. Catal. 480 (2020) 110525
[37] Z. Wu, X.X. Zhao, J. Zhang, X. Li, Y. Zhang, F. Wang, Ethanol/1,4-dioxane/formic acid as synergistic solvents for the conversion of lignin into high-value added phenolic monomers, Bioresour. Technol. 278 (2019) 187–194
[38] W.Z. Li, X.M. Dou, C.F. Zhu, J.D. Wang, H.M. Chang, H. Jameel, X.S. Li, Production of liquefied fuel from depolymerization of kraft lignin over a novel modified nickel/H-beta catalyst, Bioresour. Technol. 269 (2018) 346–354
[39] M.A. Ebiad, D.R. Abd El–Hafiz, R.A. Elsalamony, L.S. Mohamed, Ni supported high surface area CeO2–ZrO2 catalysts for hydrogen production from ethanol steam reforming, RSC Adv. 2 (21) (2012) 8145–8156
[40] A. Bjeli?, M. Grilc, B. Likozar, Bifunctional metallic-acidic mechanisms of hydrodeoxygenation of eugenol as lignin model compound over supported Cu, Ni, Pd, Pt, Rh and Ru catalyst materials, Chem. Eng. J. 394 (2020) 124914
[41] N.A. Fathurrahman, C.S. Wibowo, M. Nasikin, M. Khalil, Optimization of sorbitan monooleate and γ-Al2O3 nanoparticles as cold-flow improver in B30 biodiesel blend using response surface methodology (RSM), J. Ind. Eng. Chem. 99 (2021) 271–281
[42] T.I. Bhuiyan, P. Arudra, M.N. Akhtar, A.M. Aitani, R.H. Abudawoud, M.A. Al-Yami, S.S. Al-Khattaf, Metathesis of 2-butene to propylene over W-mesoporous molecular sieves: A comparative study between tungsten containing MCM-41 and SBA-15, Appl. Catal. A: Gen. 467 (2013) 224–234
[43] I. Jiménez-Morales, J. Santamaría-González, P. Maireles-Torres, A. Jiménez-López, Zirconium doped MCM-41 supported WO3 solid acid catalysts for the esterification of oleic acid with methanol, Appl. Catal. A: Gen. 379 (1–2) (2010) 61–68
[44] C. Temvuttirojn, Y. Poo-Arporn, N. Chanlek, C.K. Cheng, C.C. Chong, J. Limtrakul, T. Witoon, Role of calcination temperatures of ZrO2 support on methanol synthesis from CO2 hydrogenation at high reaction temperatures over ZnOx/ZrO2 catalysts, Ind. Eng. Chem. Res. 59 (13) (2020) 5525–5535
[45] W.J. Li, P.M. Da, Y.Y. Zhang, Y.C. Wang, X. Lin, X.G. Gong, G.F. Zheng, WO3 nanoflakes for enhanced photoelectrochemical conversion, ACS Nano 8 (11) (2014) 11770–11777
[46] S. Totong, P. Daorattanachai, N. Laosiripojana, R. Idem, Catalytic depolymerization of alkaline lignin to value-added phenolic-based compounds over Ni/CeO2–ZrO2 catalyst synthesized with a one-step chemical reduction of Ni species using NaBH4 as the reducing agent, Fuel Process. Technol. 198 (2020)106248
[47] K. Barta, G.R. Warner, E.S. Beach, P.T. Anastas, Depolymerization of organosolv lignin to aromatic compounds over Cu-doped porous metal oxides, Green Chem. 16 (1) (2014) 191–196
[48] J.A. Onwudili, P.T. Williams, Catalytic depolymerization of alkali lignin in subcritical water: Influence of formic acid and Pd/C catalyst on the yields of liquid monomeric aromatic products, Green Chem. 16 (11) (2014) 4740–4748
[49] A. Kloekhorst, S. Yu, Y.E. Yao, F. Ma, H.J. Heeres, Catalytic hydrodeoxygenation and hydrocracking of Alcell? lignin in alcohol/formic acid mixtures using a Ru/C catalyst, Biomass Bioenergy 80 (2015) 147–161
[50] X.Y. Lu, X.J. Zhu, H.Q. Guo, H. Que, D.D. Wang, D.X. Liang, T. He, C.J. Hu, C.Z.Xu, X.L. Gu, Efficient depolymerization of alkaline lignin to phenolic compounds at low temperatures with formic acid over inexpensive Fe–Zn/Al2O3 catalyst, Energy Fuels 34 (6) (2020) 7121–7130
[51] S.O. Limarta, H. Kim, J.M. Ha, Y.K. Park, J. Jae, High-quality and phenolic monomer-rich bio-oil production from lignin in supercritical ethanol over synergistic Ru and Mg–Zr-oxide catalysts, Chem. Eng. J. 396 (2020) 125175
[52] J.L. Wen, B.L. Xue, F. Xu, R.C. Sun, A. Pinkert, Unmasking the structural features and property of lignin from bamboo, Ind. Crop. Prod. 42 (2013) 332–343
[53] A.K. Deepa, P.L. Dhepe, Lignin depolymerization into aromatic monomers over solid acid catalysts, ACS Catal. 5 (1) (2015) 365–379

Insights into depolymerization pathways and mechanism of alkali lignin over a Ni_1.2–ZrO₂/WO₃/γ-Al₂O₃ catalyst

Insights into depolymerization pathways and mechanism of alkali lignin over a Ni_1.2–ZrO₂/WO₃/γ-Al₂O₃ catalyst

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