Experimental and Theoretical Studies on the Pyrolysis Mechanism of β-1-Type Lignin Dimer Model Compound

Jiang, Xiaoyan; Lü, Qiang; Ye, Xiaoning; Hu, Bin; Chen, Dong

doi:10.15376/biores.11.3.6232-6243

Cited by 11 publications

(12 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In addition, both homolysis and concerted reactions for the rupture of the typical C–C-linked lignin dimers have also been examined by QC modeling. One homolytic plus three concerted breakage patterns of the C α –C β bond have been reported for the β–1-type lignin dimers, such as 1,2-bis(3,5-dimethoxyphenyl)propane-1,3-diol and 1,2- p -hydroxyphenyl-1,3-propanediol (reactions 1–4 in Figure b). , At low temperatures, the concerted breakage through cyclic Grob fragmentation (reaction 3) has the lowest energy barrier, whereas the C α –C β homolysis exceeds the concerted reactions when the temperature is up to 1300 K . On the basis of the Py–GC/MS experiments and DFT results, it has been proposed that the concerted reactions 3 and 4 are dominant and the C α –C β homolysis reaction 1 is less competitive, while the concerted reaction 2 is almost impossible .…”

Section: Pyrolysis Mechanism Of Ligninmentioning

confidence: 82%

“…Beyond the work of Beste et al on the lignin pyrolysis mechanisms, Beckham et al and Gnanakaran et al focused on the BDEs of the homolysis of distinct linkages in more than 60 different lignin dimers. Our team − also looked into the possible breakage of different linkages in lignin dimers. Different from the reports of Beckham et al and Gnanakaran et al, our work carefully explored the concerted breakage of the linkages and the subsequent decomposition pathways following the depolymerization.…”

Section: Qc Modeling and Its Application To Biomass Pyrolysismentioning

confidence: 99%

“…In comparison to the monomers, the dimer models have attracted much more attention when exploring the role of the linkages and substituents in lignin pyrolysis. Phenethyl phenyl ether (PPE), the simplest β–O–4-linked lignin dimer without any substituents, has been widely discussed in both QC modeling and experiments. ,, On the basis of the natural structure of lignin, by attaching hydroxyl and/or methoxy groups to the two aromatic rings or introducing hydroxyl and/or hydroxymethyl moieties to the C α and C β sites, different β–O–4-linked dimers have also been reported. ,, Also, lignin dimers linked by α–O–4, ,− β–1, , and β–5 , bonds and substituted by various functional groups, such as benzyl phenyl ether (BPE), 1,2-diphenylethane and 2-phenyl-1-benzofuran derivatives have also been investigated in lignin pyrolysis mechanism studies. All of these lignin dimers have been playing vital roles in exploring the primary decomposition reactions.…”

Section: Biomass Structures and Modelingmentioning

confidence: 99%

See 2 more Smart Citations

Recent Progress in Quantum Chemistry Modeling on the Pyrolysis Mechanisms of Lignocellulosic Biomass

et al. 2020

Self Cite

View full text Add to dashboard Cite

Pyrolysis of lignocellulose biomass to produce various fuels and chemicals has gained increasing interest in recent decades. An in-depth understanding of the biomass pyrolysis reaction mechanisms is essential for the advancement of pyrolysis techniques. Quantum chemistry (QC) modeling is a powerful approach for the pyrolysis mechanism investigation at the atomic/molecular level. Despite a short history of only about 2 decades, its application to the biomass pyrolysis mechanism exploration has been well-developed, along with the fast advances of supercomputer and computational codes in the new century. This review addresses the recent progress on the pyrolysis mechanism of the three basic biomass components (cellulose, hemicellulose, and lignin) by QC modeling. On the basis of the QC modeling results reported in the literature, the current review critically summarizes the key developments about the pyrolysis chemistry of biomass by focusing on their microscopic elementary reactions, the formation routes of typical products, bimolecular interactions within or between biomass components, and catalytic effects of various catalysts. Notably, there are great gaps between the theoretical models employed in QC modeling and the natural biomass substance in the pyrolysis process. Therefore, a brief analysis of the challenges and future research perspectives is provided for the biomass pyrolysis mechanism research.

show abstract

Section: Pyrolysis Mechanism Of Ligninmentioning

confidence: 82%

Section: Qc Modeling and Its Application To Biomass Pyrolysismentioning

confidence: 99%

Section: Biomass Structures and Modelingmentioning

confidence: 99%

See 1 more Smart Citation

Recent Progress in Quantum Chemistry Modeling on the Pyrolysis Mechanisms of Lignocellulosic Biomass

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…Analogously, Liu et al − and Huang et al proposed decomposition pathways for model compounds, such as guaiacol and 4-benzyloxyphenol, and the dissociation of α-O-4 bonded dimers via experimental and computational means. Also, using the same methodology, Jiang et al . analyzed the initial decomposition products of 1,2-bis(3,5-dimethoxyphenyl)propane-1,3-diol, probing several competing pathways for initial decomposition of the reactant molecule.…”

Section: Mechanism and Kineticsmentioning

confidence: 99%

Progress in Modeling of Biomass Fast Pyrolysis: A Review

Kostetskyy

Broadbelt

2020

Energy Fuels

View full text Add to dashboard Cite

Fast pyrolysis of biomass is an important technology in the conversion of lignocellulosic feedstocks to value-added fuels and chemicals. Significant efforts have been dedicated to modeling of these processes to improve the viability of large-scale operation through reactor design, feedstock selection and processing, and optimization of operating conditions, among others. This work is a review of the current progress in the field of modeling of biomass fast pyrolysis processes across multiple length and time scales. Enclosed are summaries of the current state of the art in atomistic and kinetic modeling of biomass fast pyrolysis toward production of fuels and chemicals. Decomposition of aggregate biomass and its individual components was reviewed for models at various scales, highlighting important considerations. Recent applications of machine learning methods to couple multiscale phenomena with the goal of reducing computational complexity were also included. Historical context was provided for existing models and correlations, highlighting some of those most widely applied. Some of the shortcomings and bottlenecks in existing models were identified as areas for further study. Finally, potential future directions for the field are suggested with the goal of improving the viability and sustainability of pyrolysis processes and the applications of multiscale modeling toward this goal.

show abstract

“…In order to develop more efficient selective pyrolysis techniques, lignin pyrolysis mechanism and products formation pathways should be deeply uncovered to help provide a theoretical basis for directional control of the lignin pyrolysis process. Density functional theory (DFT) method is an effective tool to reveal the lignin pyrolysis mechanism at a micro level [ 13 , 14 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

A Comprehensive Study on Pyrolysis Mechanism of Substituted β-O-4 Type Lignin Dimers

Jiang

Lü

et al. 2017

IJMS

Self Cite

View full text Add to dashboard Cite

In order to understand the pyrolysis mechanism of β-O-4 type lignin dimers, a pyrolysis model is proposed which considers the effects of functional groups (hydroxyl, hydroxymethyl and methoxyl) on the alkyl side chain and aromatic ring. Furthermore, five specific β-O-4 type lignin dimer model compounds are selected to investigate their integrated pyrolysis mechanism by density functional theory (DFT) methods, to further understand and verify the proposed pyrolysis model. The results indicate that a total of 11 pyrolysis mechanisms, including both concerted mechanisms and homolytic mechanisms, might occur for the initial pyrolysis of the β-O-4 type lignin dimers. Concerted mechanisms are predominant as compared with homolytic mechanisms throughout unimolecular decomposition pathways. The competitiveness of the eleven pyrolysis mechanisms are revealed via different model compounds, and the proposed pyrolysis model is ranked in full consideration of functional groups effects. The proposed pyrolysis model can provide a theoretical basis to predict the reaction pathways and products during the pyrolysis process of β-O-4 type lignin dimers.

show abstract

Experimental and Theoretical Studies on the Pyrolysis Mechanism of β-1-Type Lignin Dimer Model Compound

Cited by 11 publications

References 19 publications

Recent Progress in Quantum Chemistry Modeling on the Pyrolysis Mechanisms of Lignocellulosic Biomass

Recent Progress in Quantum Chemistry Modeling on the Pyrolysis Mechanisms of Lignocellulosic Biomass

Progress in Modeling of Biomass Fast Pyrolysis: A Review

A Comprehensive Study on Pyrolysis Mechanism of Substituted β-O-4 Type Lignin Dimers

Contact Info

Product

Resources

About