Density functional theory study on the effect of C<sub><i>α</i></sub>-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer

DUAN Yu; CHENG Hao; WU Shu-bin

Volume 47 Issue 12

Dec. 2019

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Article Navigation > Journal of Fuel Chemistry and Technology > 2019 > 47(12): 1440-1449

DUAN Yu, CHENG Hao, WU Shu-bin. Density functional theory study on the effect of Cα-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer[J]. Journal of Fuel Chemistry and Technology, 2019, 47(12): 1440-1449.

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DUAN Yu, CHENG Hao, WU Shu-bin. Density functional theory study on the effect of C_α-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer[J]. Journal of Fuel Chemistry and Technology, 2019, 47(12): 1440-1449.

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Density functional theory study on the effect of C_α-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer

DUAN Yu^{1, 2},
CHENG Hao^{1, 2},
WU Shu-bin^{1, 2
,
,}

1.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
2.
Experimental Teaching Demonstration Center of Light Industry and Food Science, South China University of Technology, Guangzhou 510640, China

Funds:

the Natural Sciences Foundation of China 31870558

the Natural Sciences Foundation of China 31670582

More Information

Corresponding author: WU Shu-bin, Tel: 020-22236808, E-mail: shubinwu@scut.edu.cn
Received Date: 2019-08-29
Rev Recd Date: 2019-11-05

Available Online: 2021-01-23

Publish Date: 2019-12-10

Abstract

Abstract

Density functional theory method was used to calculate the bond dissociation energies of the C_aromatic-C_α, C_α-C_β, C_β-O bond, and C_aromatic-O bonds in four lignin dimer model compounds, viz., (2-(2-methoxyphenoxy)-1-phenylethan-1-ol, 2-(2-methoxyphenoxy)-1-phenylethan-1-one, 1-methoxy-2-(2-methoxy-2-phenylethoxy)benzene, and 2-(2-methoxyphenoxy)-1-phenylethyl acetate; the homolytic cracking reaction during pyrolysis of these dimers was then invetigated and the formation pathways of pyrolysis products of different dimers were analyzed. The results show that the homogenization of C_β-O bond is the main reaction in the initial pyrolysis of dimer, whereas the homolysis of C_α-C_β bond is a competitive reaction. After the oxidation and acetylation of C_α-OH, the bond dissociation energy of C_β-O bond decreases, whereas the dissociation energy of C_α-C_β bond increases, ccompanied with an increase in the probability of the C_β-O bond dissociation and a decrease in the competitive ability of C_α-C_β bond homolysis. For the pyrolysis of four model compounds, the main aromatic products include benzyl alcohol, toluene, benzaldehyde, guaiacol, etc. The selective modification of the C_α-OH functional groups can regulate the types of pyrolysis products. In particular, the product types for the pyrolysis of model compounds modified by oxidation become less, accompanied with an increase in the selectivity to ceratin products. Ethylbenzene and toluene can be produced from the hydrolysis of dimers modified by methylation and acetylation.
- lignin,
- pyrolysis,
- homolysis,
- C_α-OH functional group,
- β-O-4 bonding,
- density functional theory

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References(33)

References

[1]	LIU X, WEI W, WU S, LEI M, LIU Y. A promptly approach from monosaccharides of biomass to oligosaccharides via sharp-quenching thermo conversion (SQTC)[J]. Carbohydr Polym, 2018, 189:204-209. doi: 10.1016/j.carbpol.2018.01.107
[2]	LEI M, WU S, LIANG J, LIU C. Comprehensive understanding the chemical structure evolution and crucial intermediate radical in situ observation in enzymatic hydrolysis/mild acidolysis lignin pyrolysis[J]. J Anal Appl Pyrolysis, 2019, 138:249-260. doi: 10.1016/j.jaap.2019.01.004
[3]	ZOU R, WANG Y, JIANG L, YU Z, ZHAO Y, WU Q, DAI L, KE L, LIU Y, RUAN R. Microwave-assisted co-pyrolysis of lignin and waste oil catalyzed by hierarchical ZSM-5/MCM-41 catalyst to produce aromatic hydrocarbons[J]. Bioresour Technol, 2019, 289:121609. doi: 10.1016/j.biortech.2019.121609
[4]	SHUAI L, AMIRI M T, QUESTELL-SANTIAGO Y M, HEROGUEL F, LI Y, KIM H, MEILAN R, CHAPPLE C, RALPH J, LUTERBACHER J S. Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization[J]. Science, 2016, 354(6310):329-333. doi: 10.1126/science.aaf7810
[5]	RAGAUSKAS A J, BECKHAM G T, BIDDY M J, CHANDRA R, CHEN F, DAVIS M F, DAVISON B H, DIXON R A, GILNA P, KELLER M, LANGAN P, NASKAR A K, SADDLER J N, TSCHAPLINSKI T J, TUSKAN G A, WYMAN C E. Lignin valorization:Improving lignin processing in the biorefinery[J]. Science, 2014, 344(6185):1246843. doi: 10.1126/science.1246843
[6]	DAI G, ZHU Y, YANG J, PAN Y, WANG G, WANG S, REUBROYCHAROEN P. Mechanism study on the pyrolysis of the typical ether linkages in biomass[J]. Fuel, 2019, 249:146-153. doi: 10.1016/j.fuel.2019.03.099
[7]	HA J, HWANG K, KIM Y, JAE J, KIM K H, LEE H W, KIM J, PARK Y. Recent progress in the thermal and catalytic conversion of lignin[J]. Renewable Sustainable Energy Rev, 2019, 111:422-441. doi: 10.1016/j.rser.2019.05.034
[8]	WANG S, DAI G, YANG H, LUO Z. Lignocellulosic biomass pyrolysis mechanism:A state-of-the-art review[J]. Prog Energy Combust, 2017, 62:33-86. doi: 10.1016/j.pecs.2017.05.004
[9]	ARO T, FATEHI P. Production and application of lignosulfonates and sulfonated lignin[J]. ChemSusChem, 2017, 10(9):1861-1877. doi: 10.1002/cssc.201700082
[10]	LORA J H, GLASSER W G. Recent industrial applications of lignin:A sustainable alternative to nonrenewable materials[J]. J Polym Environ, 2002, 10(1):39-48. http://cn.bing.com/academic/profile?id=cea4d37e14c1dce746b84bbd574ad545&encoded=0&v=paper_preview&mkt=zh-cn
[11]	KAWAMOTO H, RYORITANI M, SAKA S. Different pyrolytic cleavage mechanisms of β-ether bond depending on the side-chain structure of lignin dimers[J]. J Anal Appl Pyrolysis, 2008, 81(1):88-94. doi: 10.1016/j.jaap.2007.09.006
[12]	CHEN Y, FANG Y, YANG H, XIN S, ZHANG X, WANG X, CHEN H. Effect of volatiles interaction during pyrolysis of cellulose, hemicellulose, and lignin at different temperatures[J]. Fuel, 2019, 248:1-7. doi: 10.1016/j.fuel.2019.03.070
[13]	KAWAMOTO H, NAKAMURA T, SAKA S. Pyrolytic cleavage mechanisms of lignin-ether linkages:A study on p-substituted dimers and trimers[J]. Holzforschung, 2008, 62(1):50-56. doi: 10.1515/HF.2008.007
[14]	YERRAYYA A, SURIAPPARAO D V, NATARAJAN U, VINU R. Selective production of phenols from lignin via microwave pyrolysis using different carbonaceous susceptors[J]. Bioresour Technol, 2018, 270:519-528. doi: 10.1016/j.biortech.2018.09.051
[15]	JIANG W, WU S, LUCIA L A, CHU J. A comparison of the pyrolysis behavior of selected β-O-4 type lignin model compounds[J]. J Anal Appl Pyrolysis, 2017, 125:185-192. doi: 10.1016/j.jaap.2017.04.003
[16]	JIANG W, CHU J, WU S, LUCIA L A. Modeling pyrolytic behavior of pre-oxidized lignin using four representative β-ether-type lignin-like model polymers[J]. Fuel Process Technol, 2018, 176:221-229. doi: 10.1016/j.fuproc.2018.03.041
[17]	KIM J, HAFEZI-SEFAT P, CADY S, SMITH R G, BROWN R C. Premethylation of lignin hydroxyl functionality for improving storage stability of oil from solvent liquefaction[J]. Energy Fuels, 2019, 33(2):1248-1255. doi: 10.1021/acs.energyfuels.8b03894
[18]	ZHU G, QIU X, ZHAO Y, QIAN Y, PANG Y, OUYANG X. Depolymerization of lignin by microwave-assisted methylation of benzylic alcohols[J]. Bioresour Technol, 2016, 218:718-722. doi: 10.1016/j.biortech.2016.07.021
[19]	LOHR T L, LI Z, MARKS T J. Selective ether/ester C-O cleavage of an acetylated lignin model via tandem catalysis[J]. ACS Catal, 2015, 5(11):7004-7007. doi: 10.1021/acscatal.5b01972
[20]	HUANG J, LIU C, WU D, TONG H, REN L. Density functional theory studies on pyrolysis mechanism of β-O-4 type lignin dimer model compound[J]. J Anal Appl Pyrolysis, 2014, 109:98-108. doi: 10.1016/j.jaap.2014.07.007
[21]	BRITT P F, BUCHANAN A C, COONEY M J, MARTINEAU D R. Flash vacuum pyrolysis of methoxy-substituted lignin model compounds[J]. J Org Chem, 2000, 65(5):1376-1389. doi: 10.1021/jo991479k
[22]	BESTE A, BUCHANAN A C, BRITT P F, HATHORN B C, HARRISON R J. kinetic analysis of the pyrolysis of phenethyl phenyl ether:Computational prediction of α/β-selectivities[J]. J Phys Chem A, 2007, 111:12118-12126 doi: 10.1021/jp075861+
[23]	BRITT P F, KIDDER M K, BUCHANAN A C. Oxygen substituent effects in the pyrolysis of phenethyl phenyl ethers[J]. Energy Fuels, 2007, 21(6):3102-3108. doi: 10.1021/ef700354y
[24]	HUANG X, LIU C, HUANG J, LI H. Theory studies on pyrolysis mechanism of phenethyl phenyl ether[J]. Comput Theor Chem, 2011, 976(1/3):51-59. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=2dbfa3d97330434573be123ae336e556
[25]	CHEN L, YE X, LUO F, SHAO J, LU Q, FANG Y, WANG X, CHEN H. Pyrolysis mechanism of β-O-4 type lignin model dimer[J]. J Anal Appl Pyrolysis, 2015, 115:103-111. doi: 10.1016/j.jaap.2015.07.009
[26]	ASARE S O, HUANG F, LYNN B C. Characterization and sequencing of lithium cationized β-O-4 lignin oligomers using higher-energy collisional dissociation mass spectrometry[J]. Anal Chim Acta, 2019, 1047:104-114. doi: 10.1016/j.aca.2018.09.068
[27]	JARVIS M W, DAILY J W, CARSTENSEN H, DEAN A M, SHARMA S, DAYTON D C, ROBICHAUD D J, NIMLOS M R. Direct detection of products from the pyrolysis of 2-phenethyl phenyl ether[J]. J Phys Chem A, 2011, 115(4):428-438. doi: 10.1021/jp1076356
[28]	FRISCH M J, TRUCKS G W, SCHLEGEL H B, et al. Gaussian09[CP]. Gaussian, Inc.Pittsburgh PA, 2009.
[29]	ELDER T. A computational study of pyrolysis reactions of lignin model compounds[J]. Holzforschung, 2010, 64(4). http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=7cce4c80ce24895d747a7bc532b60c7c
[30]	JIANG X, LU Q, HU B, LIU J, DONG C, YANG Y. Intermolecular interaction mechanism of lignin pyrolysis:A joint theoretical and experimental study[J]. Fuel, 2018, 215:386-394. doi: 10.1016/j.fuel.2017.11.084
[31]	BESTE A, BUCHANAN A C. Substituent effects on the reaction rates of hydrogen abstraction in the pyrolysis of phenethyl phenyl ethers[J]. Energy Fuels, 2010, 24(5):2857-2867. doi: 10.1021/ef1001953
[32]	PARTHASARATHI R, ROMERO R A, REDONDO A, GNANAKARAN S. Theoretical study of the remarkably diverse linkages in lignin[J]. J Phys Chem Lett, 2011, 2(20):2660-2666. doi: 10.1021/jz201201q
[33]	BESTE A, BUCHANAN A C. Kinetic simulation of the thermal degradation of phenethyl phenyl ether, a model compound for the β-O-4 linkage in lignin[J]. Chem Phys Lett, 2012, 550:19-24. doi: 10.1016/j.cplett.2012.08.040