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A new insight into pyrolysis mechanism of three typical actual biomass:

the influence of structural differences on pyrolysis process

Guanyu Wang, Gongxin Dai, Shaoqiu Ding, Jingfeng Wu, Shurong

Wang

PII: S0165-2370(21)00170-4
DOI: https://doi.org/10.1016/j.jaap.2021.105184
Reference: JAAP 105184

To appear in: Journal of Analytical and Applied Pyrolysis

Received Date: 28 February 2021

Revised Date: 13 April 2021
Accepted Date: 17 April 2021

Please cite this article as: Wang G, Dai G, Ding S, Wu J, Wang S, A new insight into pyrolysis
mechanism of three typical actual biomass: the influence of structural differences on pyrolysis
process, Journal of Analytical and Applied Pyrolysis (2021),
doi: https://doi.org/10.1016/j.jaap.2021.105184

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A new insight into pyrolysis mechanism of three typical actual biomass: the influence

of structural differences on pyrolysis process

Guanyu Wanga#, Gongxin Daib#, Shaoqiu Dinga, Jingfeng Wua, Shurong Wanga,* srwang@zju.edu.cn

a
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou

310027, China

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b
Shanghai Electric Group Co., Ltd. Central Academe, Shanghai 200070, China

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 Corresponding author: Shurong Wang at: State Key Laboratory of Clean Energy Utilization, Zhejiang University, Zheda Road 38, Hangzhou
310027, China. Tel.: +86 571 87952801; fax: +86 571 87951616. E-mail address:.

# These authors contributed equally to this work.

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Highlights
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 The structural differences of biomass had significant influence on pyrolysis mechanism.
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 Cleavage of glycosidic bond and dissociation of O-acetyl group in softwood hemicellulose were prone

to occur.
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 The breakage of α-ether bond of hemicellulose-lignin bonds mainly occurred via Cα-O concerted

cleavage.
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Abstract:

Biomass pyrolysis involves complex structural changes and numerous chemical reactions. At present, most

studies on actual biomass pyrolysis focus on the macroscopic thermal degradation process, while the studies on

microscopic pyrolysis rules are still very limited. This work provides a new insight into the pyrolysis mechanism

of three types of actual biomass, namely hardwood (eucalyptus saligna), softwood (pinus sylvestris) and straw
(corn straw), by combining in-situ characterization of the evolution of biomass structures with density

functional theory (DFT) calculations of pyrolysis pathways. Firstly, the evolution of various characteristic

structures during biomass pyrolysis was monitored by in-situ diffuse reflectance infrared Fourier transform

spectroscopy (in-situ DRIFT). It was found that the thermal stability of the same functional group in different

biomass samples are not exactly the same, and the structural differences in biomass would lead to different

pyrolysis behaviors. Then, considering the great structural difference of hemicellulose in different biomass, the

key initial pyrolysis reaction paths including the cleavage of glycosidic bonds, the dissociation of side chains

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and the opening of sugar ring of hemicellulose were studied by DFT calculations. It was found that the cleavage

of glycosidic bonds and the dissociation of O-acetyl side chains of glucomannan in softwood hemicellulose are

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more advantageous than those of xylan in hardwood and straw hemicellulose. In addition, the cleavage
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mechanism of hemicellulose-lignin bond (LC), a characteristic connection structure between different

components of actual biomass, was investigated. The result showed that the cleavage of Cα-O mainly occurred
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by concerted mechanism for α-ether bond of LC.
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Keywords: Actual biomass; Pyrolysis mechanism; Structural characteristics; In-situ characterization; DFT
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calculations

1 Introduction
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With the growth of the consumption of bioenergy worldwide, the utilization of biomass energy has become
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more diversified [1,2]. Besides the traditional combustion for production of electricity and heat, more and more

biomass are converted into low-carbon biofuels or biochemicals by methods without the existence of “flame”

[3,4]. Pyrolysis is an important "flameless" conversion method for the utilization of all components of biomass.

Obviously, the optimization and improvement of pyrolysis technology is of great significance to the recycling

of waste biomass and the construction of low-carbon energy society. The fundamental researches on the
mechanism of biomass pyrolysis will be helpful to clarify biomass pyrolysis process and promote the

development of biomass pyrolysis technology.

Lignocellulosic biomass is mainly composed of cellulose, hemicellulose and lignin, which are cross-linked

with each other [1,5-7]. The structural complexity and component diversity of actual biomass bring certain

difficulties to its pyrolysis mechanism study. Currently, most researches tend to explore the pyrolysis rules of

individual component of biomass, and further deduce and summarize the pyrolysis mechanism of actual

biomass [3,6-9]. Wang et al. [10] thoroughly analyzed the structural differences of softwood hemicellulose and

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hardwood hemicellulose and their pyrolysis process based on the minimally damaged hemicellulose polymers

extracted from different biomass samples. They reported that hardwood hemicellulose was mainly composed

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of pentoses, and furfural was the major pyrolysis product, while softwood hemicellulose was mainly composed
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of hexoses, and its pyrolysis products contain more anhydrosugars and 5-hydroxymethylfurfural. Based on in-

situ EPR characterization, Lei et al. [11] found that softwood lignin contained more guaiacyl units compared
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with hardwood lignin, which could generate more free radicals in pyrolysis. Obviously, the structures of
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different types of biomass are quite different, and the structures of extracted components are also different from

that of raw biomass. Besides, the studies on pyrolysis mechanism of individual components ignore the
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interactions between biomass components.

The method by combining experimental characterization and theoretical calculation can provide more
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objective and convincing results, and has been widely used in the mechanism studies of biomass pyrolysis
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[6,7,12,13]. In-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFT) is an excellent

in-situ characterization method, which can effectively obtain real-time information about the changes of

biomass structures during pyrolysis, and DFT calculations can be used to study the possible pyrolysis reaction

paths of biomass and obtain related kinetic parameters [6]. Hu et al. [9] found that the release of large amounts

of volatiles was often accompanied by the drastic evolution of functional groups in the solid residues during

xylan pyrolysis by combining in-situ DRIFT and DFT calculations, and the dissociation of side chains such as
arabinose in xylan was more likely to occur than the cleavage of the main chain. Dai et al. [7] investigated the

evolution of functional groups and the initial reaction pathways during the pyrolysis of xylose, xylobiose, and

xylan. They suggested that xylan with more side chains tended to generate more linear small compounds by

ring rupture reactions. However, the model compounds used in the aforementioned researches only represent

small structural fragments in biomass, and cannot reflect the influence of the overall structural differences on

pyrolysis. Direct exploration of the structural evolution of actual biomass and in-depth analysis of the reaction

pathways of the characteristic structures and linkages by DFT studies will provide valuable reference of biomass

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pyrolysis mechanism.

In this work, eucalyptus saligna (hardwood), pinus sylvestris (softwood) and corn straw (straw) were

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selected as three typical actual biomass samples. At first, in-situ DRIFT was used to monitor the evolution
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process of various functional groups in pyrolysis. Then, structural fragments with significant differences were

selected to investigate the influence of structural differences of biomass components on key reaction paths
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including depolymerization and ring opening via DFT calculations. Finally, the interactions of biomass
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components were considered, and the pyrolysis reaction pathways of typical hemicellulose-lignin bond were

investigated to further reveal the influence of structural differences in biomass on pyrolysis process.
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2 Materials and Methods

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2.1 Materials
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The biomass samples used in this study (eucalyptus saligna, pinus sylvestris and corn straw) were grinded

and screened to 40-60 mesh, and dried at 110 °C for 12 hours.

2.2 Pyrolysis behavior analysis

The three samples were placed in a high-temperature reaction chamber for pyrolysis experiments,
respectively. The temperature of the chamber was increased from 120 °C to 500 °C at a heating rate of 5 °C/min,

and the spectra at each setting temperature was collected in real time by infrared spectrometer (Nicolet, Nicolet

460, US) equipped with a diffuse reflection accessory. The relative intensity (Iv/Im) was used to represent the

change process of each functional group with temperature. It should be noted that Iv represented the vibration

intensity of each functional group, while Im is the maximum intensity among all spectra for a given functional

group.

2.3 Theoretical calculation

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All DFT calculations for pyrolysis reaction pathways involved in this study were carried out in Gaussian03

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software, and B3LYP functional was used in the whole calculation process. Due to the limitation of the

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computing capacity, the ONIOM methodology was used to reduce computational difficulty. 6-31+g(d,p) basis

set with higher accuracy was used for the key structure, while 6-31g basis set with lower accuracy was used for
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the other parts. The molecular configurations involved in the calculation process were confirmed by frequency
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calculations, in which the reactants and products did not have imaginary frequencies, while the transition states

contained only one imaginary frequency. All energy values were corrected according to zero-point energy.
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Intrinsic reaction coordinate (IRC) calculations were used to ensure that the reactants and the products can be

connected by the transition states. Besides, the standard transition state theory based on Wigner tunneling
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corrections was applied to the calculation of the reaction rate constants at different temperatures.
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3 Results and discussion

3.1 Structural evolution of the different kinds of biomass during pyrolysis

In order to clarify the influence of structural differences of different biomass on pyrolysis process, the

evolution of various functional groups in actual biomass was monitored. The in-situ DRIFT spectra of the
pyrolysis processes of eucalyptus saligna, pinus sylvestris and corn straw are shown in Figure 1. The variation

rules of the intensity of each functional group with temperature are shown in Figure 2. The attribution of each

functional group in the spectra is mainly carried out according to the references [14-16]. In the high wavenumber

region (2800-3700 cm-1), the signal at 3370 cm-1 belongs to the associated hydroxyls, while that at 3540 cm-1

belongs to free hydroxyls/hydroxyls with weak hydrogen bond. With the progress of pyrolysis reactions, the

associated hydroxyls in eucalyptus saligna are gradually transformed into free hydroxyls/hydroxyls with weak

hydrogen bond. Moreover, at the initial stage of pyrolysis, the intensity of free hydroxyls/hydroxyls with weak

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hydrogen bond increases to a certain extent, while the intensity of associated hydroxyls decreases. This indicates

that the hydrogen bonds in biomass are destroyed during pyrolysis and the conversion of associated hydroxyls

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to free hydroxyls occurs. Ru et al. [16] also observed similar phenomenon in the analysis of the structural
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changes of fast growing poplar during torrefaction. The signals at 2930 cm-1 and 2870 cm-1 are attributed to -

CH2 and -CH in alkane structures, respectively. The former mainly exists in C6 in the hexose units of cellulose
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and hemicellulose and Cγ in propane side chains of lignin, while the latter mainly exists in the sugar ring in
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monosaccharide units of cellulose and hemicellulose. Compared with the change of free hydroxyls/hydroxyls

with weak hydrogen bond, the intensity reduction of -CH2 and -CH in alkane structures occurs earlier in
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pyrolysis. Chen et al. [15] found that -CH2 connected with primary alcohols in bamboo was oxidized to generate

carbonyl and carboxyl groups at first during pyrolysis. According to the variation trend of the intensity of each
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functional group, it can be found that the change of -CH is earlier than that of -CH2, which indicates that the
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ring-opening of monosaccharide units in cellulose and hemicellulose are more prone to occur than the oxidation

of primary alcohols. In the high wavenumber region, the structural evolution processes of pinus sylvestris and

corn straw are similar to that of eucalyptus saligna. It is worth noting that the intensity of associated hydroxyls

in pinus sylvestris decrease significantly at low temperatures, and the reason for this phenomenon is that the

thermal stability of hydrogen bonds in pinus sylvestris is poor.

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Figure 1. In-situ DRIFT spectra of eucalyptus saligna, pinus sylvestris and corn straw at different pyrolysis

temperatures.
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In the C-O functional group region of the fingerprint region (800-1800 cm-1), the signal at 897 cm-1
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corresponds to C1 in glycosidic bonds of cellulose and hemicellulose. The signals at 1050 cm -1 and 1100 cm-1

are attributed to hydroxyls in primary and secondary alcohols, respectively. The signal at 1160cm-1 is mainly

attributed to C-O-C ether bonds existing in biomass, including glycosidic bonds, C-O bonds in sugar ring, ether

bonds between side chains and sugar units in hemicellulose and aryl ether linkages in lignin, while the signal at

1240cm-1 is attributed to C-O stretching vibration in cycloether and aryl alkyl ether. It can be found that the

thermal stability of glycosidic bonds is worse than that of the hydroxyls in primary and secondary alcohols
according to the tendency of their intensities with reaction temperature. Previous study on the pyrolysis of

cellulose and hemicellulose also found that the dehydration of hydroxyls in sugar ring required a higher energy

barrier and was not easy to occur [6]. Among these three actual biomass, the thermal stability of C-O ether

bonds follows: pinus sylvestris< corn straw< eucalyptus saligna. The signals at 1370 cm-1 and 1325 cm-1 belong

to methyl and methylene in biomass, respectively. Methyl mainly exists in O-acetyl and uronic acid side chains

in hemicellulose and methoxyl groups in lignin. With the proceeding of pyrolysis reactions, the dissociation of

side chains in hemicellulose and demethoxylation reactions in lignin result in the decrease of the intensity of

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methyl. The signals at 1426 and 1510 cm-1 mainly correspond to the backbone of aromatic rings. The release of

phenols during pyrolysis has a negative effect on their intensities, while the carbonization reaction will form

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new aromatic ring structures, making their intensities increase. The former has a greater effect on the aromatic
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ring structure, making the intensities of 1426 and 1510 cm-1 peaks decrease with the increase of temperature.

The signal at 1590 cm-1 is attributed to C=C stretching vibration in the structure of conjugated olefin. At the
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initial stage of pyrolysis, its intensity decreases to some extent. Then, as dehydration, dissociation of side chains,
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ring opening and other reactions proceed in the main reaction stage, its intensity increases. The signal at 1690

cm-1 is mainly attributed to C=O stretching vibration in ketones, while that at 1740 cm-1 is mainly attributed to
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C=O stretching vibration in ester and acids. The C=O peaks of ester and acid structures can be observed

obviously in the original structures of eucalyptus saligna and pinus sylvestris, while the peak in corn straw is
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not obvious. Wang et al. [10,17] found that the content of O-acetyl groups in corn straw was the lowest among
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these three actual biomass in the study on minimally damaged extracted hemicellulose. The changes of the peak

intensities of 1690 cm-1 and 1740 cm-1 in these three biomass were significantly different. For eucalyptus saligna,

the peak intensities of 1690 and 1740 cm-1 remain almost unchanged at the initial stage of pyrolysis, and then

increase to a certain extent with the increase of temperature, reaching the maximum at 360-380°C, and finally

decrease. The peak intensities of 1690 cm-1 and 1740 cm-1 in pinus sylvestris decrease obviously at the early

stage of pyrolysis, and then the variation trend is almost the same as that of eucalyptus saligna. In corn straw,
the peak intensity of 1740 cm-1 has the same variation trend as that of eucalyptus saligna, while the peak intensity

of 1690 cm-1 does not change much during the whole pyrolysis process, and only decreases to a certain extent

in terminal stage of pyrolysis. This indicates that although these three types of biomass are mainly composed

of cellulose, hemicellulose and lignin, their pyrolysis behaviors are not the same due to the structural differences.

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Figure 2. The variation trends of different functional groups with temperatures during pyrolysis of eucalyptus

saligna, pinus sylvestris and corn straw

3.2 Initial reaction pathways during biomass pyrolysis

3.2.1 Reaction pathways for different kinds of hemicellulose

In order to understand the pyrolysis process of biomass better, DFT calculations were further used to

explore the initial pyrolysis reaction paths of the structures with significant differences in different actual

biomass. Among the three components of biomass, the structure of cellulose is almost the same, while

hemicellulose and lignin are quite different. Therefore, it is necessary to study the hemicellulose pyrolysis of

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different biomass at first. Previous studies [10,17,18] indicated that hardwood hemicellulose is mainly

composed of glucuronoxylan. The main chain of glucuronoxylan is linked by xylose, and hydroxyls at C2 and

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C3 position of xylose units in the backbone can be replaced by O-acetyl groups, while uronic acid side chains

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are connected to the backbone by α-1-2 glycosidic bonds. Straw hemicellulose is mainly composed of

arabinoglucuronoxylan. Compared with glucuronoxylan, arabinoglucuronoxylan has arabinose side chains

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attached to the main chain via α-1-3 glycosidic bonds. Softwood hemicellulose is mainly composed of
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arabinoglucuronoxylan and galactoglucomannan. The main chain of galactoglucomannan is composed of

mannose and glucose, and hydroxyls at C2 and C3 positions of sugar units in the main chain can be replaced
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by O-acetyl groups. The galactose side chains can be connected to the main chain by α-1-6 glycosidic bonds.

In the previous studies, the reaction process of xylan at the early stage of pyrolysis has been systematically
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investigated[7]. It was found that the energy barriers required for the cleavage of glycosidic bonds and ring-
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opening reactions were lower during the initial pyrolysis of xylan when arabinose side chain exists, and the

energy barrier for the dissociation of arabinose side chains was lower than that of O-acetyl side chains and

uronic acid side chains. This could explain the in-situ infrared characterization result, which shows that the

thermal stability of ether bonds, such as glycosidic bonds and C-O bonds in sugar ring in eucalyptus saligna is

stronger than that of corn straw. Here, we mainly investigate the pyrolysis process of galactoglucomannan. At

the initial stage of hemicellulose pyrolysis, the main reactions include the cleavage of glycosidic bonds, direct
ring opening of sugar units, dehydration of hydroxyl groups in sugar ring and the dissociation of side chains.

Due to the high energy barrier required for the dehydration of hydroxyl groups in sugar ring [6], the cleavage

of glycosidic bonds, direct ring opening of sugar units and the dissociation of side chains are mainly studied

here.

Firstly, the pyrolysis reaction pathways of glucomannan with the presence of O-acetyl side chains are

investigated, as shown in Figure 3. The calculated energy barrier for each pathway is shown in Figure 4. The

position of O-acetyl groups has a great influence on the reaction process of glucomannan. The cleavage of

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glycosidic bonds in the main chain of glucomannan occurs via the breakage of C1-Oglycosidic bond bonds, and short

chain with levoglucosan-terminated end is formed. It can be found from Figure 4 that the thermal stability of

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glycosidic bond is stronger when O-acetyl group is located at the C2 position (G2, M2) of sugar unit compared
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with that located at the C3 position (G3, M3). Among them, when O-acetyl group is located at G2 position, the

energy barrier required is the highest, reaching 206.2 kJ/mol, while when it is located at M3 position, the energy
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barrier for the cleavage of glycosidic bond is as low as 154.0 kJ/mol. It was found in the previous study that the
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ring-opening reaction of glucose units in cellulose initiated by the cleavage of C1-O, and the pathway with C=C

generation via the migration of the hydrogen at C2 position was more favorable than that via the migration of
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the hydrogen at C5 position [6]. Therefore, when the O-acetyl group is located in glucose units, the ring-opening

reaction occurs via the former pathway, and the thermal stability of sugar unit is stronger when the O-acetyl
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group is present at G2 position. When the O-acetyl group is located in mannose units, the ring-opening reaction
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can only be proceeded via the pathway with the formation of C=O by the migration of the hydrogen at M5

position due to the difference of the monosaccharide unit configurations. Unlike glucose unit, the position of

O-acetyl group in mannose has little effect on the reaction rate of ring opening. The dissociation pathways of

the O-acetyl group in glucose unit and mannose unit are also different. Yang et al. [19] found that the

dissociation of O-acetyl group in xylose unit was more likely to occur via decarboxylation compared with the

removal of acetaldehyde. The O-acetyl groups at G2 and G3 positions are dissociated to generate acetic acid
via the abstractions of hydrogen at G3 and G2 position, respectively. When the O-acetyl group is located at M2

position, the decarboxylation reaction cannot occur since the O-acetyl group is located at the different side of

the sugar unit with the hydrogen atom in the adjacent C atom. Lu et al. [20] reported that the dehydration of the

hydroxyl at the C2 position in mannose could not occur via the abstraction of the hydrogen atom in the adjacent

C atom. At this time, the dissociation of the O-acetyl group at M2 position can only occur via the removal of

acetaldehyde with a high energy barrier of 306.5 kJ/mol, and is difficult to occur during pyrolysis. The O-acetyl

group at M3 position is dissociated by abstracting the hydrogen at M4 position to generate acetic acid. For O-

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acetyl-substituted glucomannan, the energy barrier required for the cleavage of glycosidic bond is much lower

than that of the ring opening during pyrolysis. The dissociation of the O-acetyl side chain is significantly

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influenced by the sugar units. When it is located in glucose, the energy barrier for the dissociation is lower than
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that of the cleavage of glycosidic bonds and the ring opening of sugar units. Whereas, when it is located in

mannose, the thermal stability of side chains is stronger, and the energy barrier for the dissociation is higher
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than that of the cleavage of glycosidic bonds.
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Figure 3. Reaction pathways of O-acetyl-substituted glucomannan during pyrolysis.

Figure 4. Energy barriers for the pyrolysis reaction pathways of O-acetyl-substituted glucomannan.

The initial reaction process of glucomannan with galactose side chain is further investigated, as shown in

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Fig. 5. When the galactose side chain is located at C6 (G6) position in glucose unit, the cleavage of glycosidic

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bond occurs at C1-Oglycosidic bond (Path 5-1), and the energy barrier is 166.9 kJ/mol. When it is located at C6 (M6)

position, the cleavage of glycosidic bond cannot occur to form short chain with levoglucosan-terminated end
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via hydrogen shift in hydroxyl group at M6 position as Path 5-1, due to the substitution of the hydroxyl group
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at M6 position with galactose unit. At this time, the cleavage of C1-Oglycosidic bond is carried out via hydrogen

shift at M2 position. The energy barrier is very high, reaching 385.5 kJ/mol (pre-exponential factor A=5.0×1013
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s-1), and the reaction is difficult to occur during pyrolysis. Therefore, when the galactose side chain is located
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at M6 position, the cleavage of glycosidic bond in glucomanan occurs at C4’-Oglycosidic bond (Path 6-1), and the

energy barrier is 228.2 kJ/mol. The position of the galactose side chain has a significant effect on the reaction
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rate of ring opening of sugar unit. When it is located at G6 position, the energy barrier for ring opening (Path

5-2) is 278.2 kJ/mol, which is significantly higher than that at M6 position (Path 6-2, 178.2 kJ/mol). The
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dissociation of the galactose side chain from the main chain of mannan mainly occurs via Path 5-3, Path 5-4,

Path 6-3 and Path 6-4. Compared with the dissociation to form galactose (Path 5-4 and Path 6-4), the dissociation

of galactose side chain is more likely to occur to generate anhydrosugar unit via Path 5-3 and Path 6-3, and the

corresponding energy barriers are 352.7 kJ/mol (Path 5-3), 227.8 kJ/mol (Path 5-4), 380.0 kJ/mol (Path 6-3)

and 233.9 kJ/mol (Path 6-4), respectively. By comparing the reaction rate constants of the initial pyrolysis
pathways of mannan at different temperatures, as shown in Fig. 6, it can be found that when the galactose side

chain is located at G6 position, the cleavage of glycosidic bond is the most likely to occur, followed by the

dissociation of side chain, while the ring opening of glucose unit is the most difficult to occur. When it is located

at M6 position, the reaction rate of the ring opening of mannose unit is the highest, while the reaction rates of

the cleavage of glycosidic bond and the dissociation of side chain are similar. In summary, at the initial stage of

glucomannan pyrolysis, the cleavage of glycosidic bonds in the main chain and the dissociation of O-acetyl side

chains are the most likely to occur, while the ring opening of the sugar units in the backbone is very difficult,

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and it only partially occurs at the mannose unit with galactose side chain. Compared with xylan, the cleavage

of glycosidic bonds and the dissociation of O-acetyl side chains to produce acetic acid are more favored during

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glucomannan pyrolysis, which is consistent with the result that thermal stability of C-O ether bonds in pinus

sylvestris is the weakest.

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Figure 5. Pyrolysis reaction pathways of glucomannan with galactose side chain.

Figure 6. Rate constants of reaction pathways of glucomannan with galactose side chain at different

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temperatures during pyrolysis.

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3.2.2 Reaction pathways for the breakage of the bonds between hemicellulose and lignin
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The interactions between components in actual biomass also affect the pyrolysis behavior of biomass.
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Typically, in actual biomass, hemicellulose and lignin are linked together via covalent bonds [21]. Due to the

structural differences of hemicellulose and lignin, the forms of the hemicellulose-lignin linkages (LC) are also
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different, and have an effect on biomass pyrolysis. Although the structure of lignin in different biomass differs

greatly, the breakage mechanism of LC in different actual biomass was investigated here considering that the
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breakage mechanisms of the linkages in lignin and the pyrolysis process of phenylpropane units already received
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extensive attentions [3,22-26]. Hemicellulose and lignin are mainly connected by ether bonds, among which α-

ether bonds (the ether bond formed between the α-hydroxyl in phenylpropane unit of lignin and the hydroxyl
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group in sugar unit of hemicellulose) are the common linkages [21,27]. The phenylpropane units of lignin can

be linked to the C2 and C3 positions of glucose and mannose units in glucomannan. Firstly, LC (H-G2) between

H-type phenylpropane unit and G2 is taken as an example to investigate the breakage mechanism of LC when

phenylpropane unit is located at the C2 and C3 positions in sugar unit. The cleavage of H-G2 can occur at Cα-

O and G2-O, and the cleavage mechanism includes concerted cleavage and homolytic cleavage, as shown in
Fig. 7. The calculated energy barriers for Path7-1, Path 7-2, Path 7-3 and Path 7-4 are 156.1 kJ/mol, 254.4

kJ/mol, 196.6 kJ/mol and 286.8 kJ/mol, respectively. Different from the homolytic cleavage of ether bonds such

as β-O-4 and α-O-4 in lignin [3,26], the energy barrier for the concerted cleavage of H-G2 is significantly lower

than that of the homolytic cleavage. Therefore, the breakage of LC occurs via concerted mechanism during

pyrolysis. Compared with the concerted cleavage of G2-O, the concerted cleavage of Cα-O in H-G2 is more

likely to occur during pyrolysis.

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Figure 7. Reaction pathways for the breakage of H-G2.

The Cα-O concerted cleavage process of LC between glucomannan and different phenylpropane units is
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further investigated, and the kinetic parameters of the related pathways are shown in Table 1. The type of

phenylpropane unit has a significant effect on the breakage of LC. The energy barrier for the breakage of G-G2
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is 148.7 kJ/mol, which is slightly lower than that of H-G2 (156.1 kJ/mol) and S-G2 (159.1 kJ/mol). The energy
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barrier for the breakage of G-G3 at G3 position is similar to that of G-G2 (148.4 kJ/mol), but it is obviously

lower than that of H-G3 and S-G3. Considering the pre-exponential factor, the reaction rates of the breakage of

G-G3 are 10 times faster than that of G-G2 at different temperatures. The situation is just the opposite when the

phenylpropane unit is located at M2 position in glucomannan. The energy barrier for the breakage of G-M2 is

195.0 kJ/mol, which is significantly higher than that of H-M2 and S-M2. The energy barriers for the breakage

of LC formed by different phenylpropane units at M3 position follow by S-M3< G-M3< H-M3. Glucomannan
mainly exists in softwood, and softwood lignin is mainly composed of G-type phenylpropane units, which

accounts for 90-95% of the total [2]. Therefore, the breakage process of LC between glucomannan and lignin

is mainly determined by the breakage process of G-type LC. The reaction rates of the breakage of G-type LC

at different positions in glucomannan are shown in Fig. 8. Within the whole temperature range, the reaction

rates follow: G-M2 <G-M3< G-G2 < G-G3. As for xylan, the difference of phenylpropane units have little effect

on the reaction rate of the breakage of LC when they are located at X2 position. Compared with LC in

glucomannan, the reaction rate of the breakage of LC at X2 position in xylan is similar to that of G-M3, while

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that at X3 position is lower than that of G-M3, much lower than that of G-G2 and G-G3. Thereby, the thermal

stability of LC (α-ether bond) in xylan is stronger than that in glucomannan. This result is consistent with the

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result that thermal stability of C-O ether bond in pinus sylvestris (softwood) is the weakest in the above in-situ

DRIFT characterization.
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Figure 8. Reaction rate constants of the breakage of LC formed by hemicellulose and different phenylpropane
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units at different temperatures.

Table 1. Kinetic parameters of the Cα-O concerted cleavage of LC formed by hemicellulose and different

phenylpropane units.

Position Path Ea (kJ/mol) A (s-1)

H-type 156.1 3.5×1012

G2 G-type 148.7 1.9×1012

S-type 159.1 7.0×1012

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H-type 219.2 1.0×1014

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G3 G-type 148.4 2.6×1013

S-type 184.6 3.7×1010

H-type
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172.2 4.5×1013
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M2 G-type 195.0 8.4×1011
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S-type 164.3 3.2×1012

H-type 175.5 1.4×1012

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M3 G-type 168.7 5.2×1011

S-type 151.8 1.3×1011

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H-type 173.5 1.7×1013

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X2 G-type 174.6 3.2×1013

S-type 170.4 2.6×1013

H-type 195.7 4.2×1013

X3 G-type 199.2 6.4 ×1013

S-type 202.8 3.3×1013

4 Conclusion

In this paper, in-situ characterization of the evolution of functional groups during pyrolysis was combined

with DFT calculations to investigate the influence of the component structures on biomass pyrolysis process.

The results show that at the initial stage of the pyrolysis of galactoglucomannan in softwood hemicellulose, the

cleavage of the glycosidic bond in the main chain and the dissociation of the O-acetyl group side chain in

glucose units are the most likely to occur. The ring opening of the sugar units in the backbone is very difficult,

and only partially occurs at the mannose unit with galactose side chain. Compared with xylan in hardwood and

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straw hemicellulose, the cleavage of the glycosidic bond and the dissociation of the O-acetyl group side chain

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in glucomannan require lower energy barriers and are more favored. The breakage of α-ether bond formed

between hemicellulose and phenylpropane units in lignin mainly occurs via the concerted cleavage of Cα-O.
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The thermal stability of α-ether bond in xylan is stronger than that in glucomannan, and its breakage in xylan
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occurs at higher pyrolysis temperatures. This work used actual biomass rather than model compounds as study
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object, which not only showed the structural evolution process of various functional groups in actual biomass,

but also deeply revealed the reaction pathways of different structures and the breakage mechanism of
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characteristic linkages. The results are closer to the actual biomass pyrolysis process, and contribute to the better

understanding of microscopic pyrolysis mechanism of actual biomass.

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Author statement
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Guanyu Wang: Writing- Original draft preparation, Writing - Review & Editing, Investigation.
Gongxin Dai: Writing - Review & Editing, Methodology, Investigation.
Shaoqiu Ding: Formal analysis.
Jingfeng Wu: Data curation.
Shurong Wang: Funding acquisition, Supervision, Reviewing and Editing.

Declaration of interests
The authors declare that they have no known competing financial interests or personal relationships that could have

appeared to influence the work reported in this paper.

5 Acknowledgement

This work was supported by the National Science Fund for Distinguished Young Scholars (51725603), the

Innovative Research Groups of the National Natural Science Foundation of China (51621005), and the Local

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Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N092).

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