Open Access

Tungstoborate Heteropolyacid Catalytic Framework for Lignin Liquefaction: Optimization of Product Yield and Comprehensive Component Distribution Analysis

4 Department of Mechanical Engineering, National Institute of Advanced Engineering Studies, India
4 Department of Electrical and Electronics Engineering, Indian Institute of Technological Innovation, India

Abstract

The increasing demand for renewable carbon sources has intensified research into lignin valorization as a sustainable route for producing fuels and value-added chemicals. However, the inherent structural heterogeneity and recalcitrance of lignin present major barriers to efficient depolymerization and controlled product selectivity. This study investigates a tungstoborate heteropolyacid-based catalytic framework for lignin liquefaction, emphasizing optimization of product yield and detailed analysis of product distribution. The catalytic system leverages the strong Brønsted and Lewis acidity of heteropolyacid clusters, enabling efficient cleavage of ether and carbon–carbon linkages in lignin macromolecules under controlled reaction environments. The theoretical foundation of catalyst stability and electronic structure is supported through density functional theory (DFT)-based approaches employing the Projector Augmented-Wave (PAW) method (Blöchl, 1994), ensuring accurate representation of ionic–electronic interactions in complex catalytic systems.

The study integrates insights from heterogeneous acid catalysis, biomass depolymerization pathways, and tungsten-based catalytic systems to construct a mechanistic framework for lignin liquefaction. Key reaction parameters influencing product yield, including temperature, catalyst loading, solvent environment, and reaction time, are systematically analyzed. Furthermore, the distribution of phenolic monomers, oligomers, and residual polymeric fractions is critically evaluated to understand catalytic selectivity. Results indicate that tungstoborate heteropolyacid catalysts significantly enhance lignin conversion efficiency while promoting selective formation of aromatic compounds.

The findings contribute to the development of sustainable catalytic systems for biorefinery applications, offering a scalable pathway for lignin valorization and advancing the understanding of heteropolyacid-mediated biomass transformation mechanisms.

Keywords

References

M. M. Ambursa , J. C. Juan , Y. Yahaya , Y. H. Taufiq-Yap , Y.-C. Lin , and H. V. Lee , “ A review on catalytic hydrodeoxygenation of lignin to transportation fuels by using nickel-based catalysts,” Renewable Sustainable Energy Rev. 138, 110667 (2021).
M. M. Ayed , I. Mestiri , B. Ayed , and A. Haddad , “ Synthesis and characterization of two novel inorganic/organic hybrid materials based on polyoxomolybdate clusters: (C5H5N5)2(C5H6N5)4 [(HAsO4)2Mo6O18]·11H2O and Na2(Himi)3 [SeMo6O21(CH3COO)3]·6H2O,” J. Mol. Struct. 1128, 368–377 (2017).
B. Biswas , A. Kumar , B. B. Krishna , J. Baltrusaitis , S. Adhikari , and T. Bhaskar , “ Catalytic depolymerization of lignin for the selective production of phenolic monomers over cobalt-supported calcium catalysts,” Energy Fuels 37, 3813–3824 (2023).
P. E. Blöchl , “ Projector augmented-wave method,” Phys. Rev. B 50, 17953–17979 (1994).
J. Cai , K. Li , and S. Wu , “ Recent advances in catalytic conversion of biomass derived 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid,” Biomass Bioenergy 158, 106358 (2022).
P. Duarah , D. Haldar , and M. K. Purkait , “ Technological advancement in the synthesis and applications of lignin-based nanoparticles derived from agro-industrial waste residues: A review,” Int. J. Biol. Macromol. 163, 1828–1843 (2020).
L. Faba , E. Díaz , and S. Ordóñez , “ Recent developments on the catalytic technologies for the transformation of biomass into biofuels: A patent survey,” Renewable Sustainable Energy Rev. 51, 273–287 (2015).
M. Guo , K. Li , L. Liu , H. Zhang , X. Hu , X. Min , J. Jia , and T. Sun , “ Resource utilization of spent ternary lithium-ions batteries: Synthesis of highly active manganese-based perovskite catalyst for toluene oxidation,” J. Taiwan Inst. Chem. E 102(2019), 268–275 (2019).
M. M. Heravi , T. Hosseinnejad , M. Tamimi , V. Zadsirjan , and M. Mirzaei , “ 12-Tungstoboric acid (H5BW12O40) as an efficient Lewis acid catalyst for the synthesis of chromenopyrimidine-2,5-diones and thioxochromenopyrimidin-5-ones: Joint experimental and computational study,” J. Mol. Struct. 1205, 127598 (2020).
Y. Hu , B. Tao , F. Shang , M. Zhou , D. Hao , R. Fan , D. Xia , Y. Yang , A. Pang , and K. Lin , “ Thermal decomposition of ammonium perchlorate over perovskite catalysts: Catalytic decomposition behavior, mechanism and application,” Appl. Surf. Sci. 513, 145849 (2020).
M. J. Janik , R. J. Davis , and M. Neurock , “ The relationship between adsorption and solid acidity of heteropolyacids,” Catal. Today 105, 134–143 (2005).
Z. Ju , W. Xiao , X. Yao , X. Tan , B. A. Simmons , K. L. Sale , and N. Sun , “ Theoretical study on the microscopic mechanism of lignin solubilization in Keggin-type polyoxometalate ionic liquids,” Phys. Chem. Chem. Phys. 22, 2878–2886 (2020).
R. Katahira , A. Mittal , K. McKinney , X. Chen , M. P. Tucker , D. K. Johnson , and G. T. Beckham , “ Base-catalyzed depolymerization of biorefinery lignins,” ACS Sustainable Chem. Eng. 4, 1474–1486 (2016).
I. V. Kozhevnikov , “ Sustainable heterogeneous acid catalysis by heteropoly acids,” J. Mol. Catal. A 262, 86–92 (2007).
G. Kresse and J. Furthmüller , “ Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set,” Phys. Rev. B 54, 11169–11186 (1996).
A. Kumar , B. Biswas , R. Kaur , B. B. Krishna , and T. Bhaskar , “ Hydrothermal oxidative valorisation of lignin into functional chemicals: A review,” Bioresour. Technol. 342, 126016 (2021).
I. Kurnia , S. Karnjanakom , A. Bayu , A. Yoshida , J. Rizkiana , T. Prakoso , A. Abudula , and G. Guan , “ In-situ catalytic upgrading of bio-oil derived from fast pyrolysis of lignin over high aluminum zeolites,” Fuel Process. Technol. 167, 730–737 (2017).
H. Park , J. K. Kim , U. G. Hong , Y. J. Lee , J. H. Song , and I. K. Song , “ Catalytic decomposition of lignin model compounds to aromatics over acidic catalysts,” Catal. Surv. Asia 17, 119–131 (2013).
M. T. Najafi , M. Mirzaei , and J. T. Mague , “ Structural scope of six new layered to pillar-layered hybrid inorganic–organic networks bearing [BW12O40]5− and lanthanoid-cluster; database study toward ligand role in assemblies,” CrystEngComm 18, 6724–6737 (2016).
M. M. Naron , F. X. Collard , L. Tyhoda , and J. F. Görgens , “ Influence of impregnated catalyst on the phenols production from pyrolysis of hardwood, softwood, and herbaceous lignins,” Ind. Crops Prod. 131, 348–356 (2019).
J. P. Perdew , K. Burke , and Y. Wang , “ Generalized gradient approximation for the exchange-correlation hole of a many-electron system,” Phys. Rev. B 54, 16533–16539 (1996).
V. K. Ponnusamy , D. D. Nguyen , J. Dharmaraja , S. Shobana , J. R. Banu , R. G. Saratale , S. W. Chang , and G. Kumar , “ A review on lignin structure, pretreatments, fermentation reactions and biorefinery potential,” Bioresour. Technol. 271, 462–472 (2019).
T. Shui , S. Feng , G. Chen , A. Li , Z. Yuan , H. Shui , T. Kuboki , and C. Xu , “ Synthesis of sodium carboxymethyl cellulose using bleached crude cellulose fractionated from cornstalk,” Biomass Bioenergy 105, 51–58 (2017).
R. Tokarz-Sobieraj , R. Grybos , U. Filek , A. Micek-Ilnicka , P. Niemiec , A. Kirpsza , and M. Witko , “ Generation of acidic sites in Al, Ga, In salts of molybdenum and tungsten Keggin-type heteropolyacids. DFT modeling and catalytic tests,” Catal. Today 257, 72–79 (2015).
A. Wang and T. Zhang , “ One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts,” Acc. Chem. Res. 46(7), 1377–1386 (2013).
M.-Y. Zheng , A.-Q. Wang , N. Ji , J.-F. Pang , X.-D. Wang , and T. Zhang , “ Transition metal–tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol,” ChemSusChem 3, 63–66 (2010).
Y. H. P. Zhang , “ Reviving the carbohydrate economy via multi-product lignocellulose biorefineries,” J. Ind. Microbiol. Biotechnol. 35, 367–375 (2008).
L. Zhou , A. Wang , C. Li , M. Zheng , and T. Zhang , “ Selective production of 1,2-propylene glycol from Jerusalem artichoke tuber using Ni-W(2)C/AC catalysts,” ChemSusChem 5, 932–938 (2012).

Similar Articles

You may also start an advanced similarity search for this article.