Energy Conversion and Management 216 (2020) 112777

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Energy Conversion and Management

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Pyrolysis behavior and product distributions of biomass six group T

components: Starch, cellulose, hemicellulose, lignin, protein and oil
Peijie Zonga,b, Yuan Jianga,b, Yuanyu Tiana,b, Jie Lia,b, Meng Yuana,b, Yaoyao Jia,b,
Minshen Chena,b, Dawei Lia,b,c, Yingyun Qiaoa,b,
⁎

a
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, China
b
Shandong Engineering and Technology Research Center of High Carbon Low Carbonization, China University of Petroleum (East China), Qingdao 266580, China
c
CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

ARTICLE INFO ABSTRACT

Keywords: Pyrolysis of more biomass group components should be studied in order to obtain a more comprehensive un-
Biomass component derstanding of various biomass pyrolysis. In this study, chemical properties of six biomass group components,
Pyrolysis namely, starch, cellulose, Hemicellulose (Hem), lignin, protein and oil, were evaluated and their pyrolysis be-
Kinetics havior, gaseous product evolution, kinetics and product distributions were investigated using TG-FTIR and Py-
TG-FTIR
GC/MS. The results indicated that their devolatilization sensitivity to heating rate followed the order of
Py-GC/MS
Hem > starch > oil > cellulose ≈ protein > lignin. Kinetic results revealed that it was difficult to pyrolyze
for biomass rich in oil and lignin but easy to pyrolyze for biomass rich in cellulose, starch, Hem and protein.
During their pyrolysis, polysaccharides (starch, cellulose and Hem) mainly generated oxygen-containing com-
ponents such as C]O and O-heterocycles; lignin mainly contributed to the formation of phenols (up to 81.4%);
protein produced nitrogen-containing components (up to 52.71%), including N-heterocycles, pyrroles, pyridines,
nitriles, and amines/amides; oil generated large quantities of alkenes (46.48%). Finally, this research would
serve to gain further insight into biomass pyrolysis containing different group components.

1. Introduction Biomass consists of all living organisms and their wastes [7]. Hence,
a large number of feedstocks are suitable for fast pyrolysis, such as
Biomass, a sustainable and CO2-neutral resource, is a chemical lignocellulosic waste, food waste and marine algae [8]. For the best use
feedstock to produce bio-oil and an attractive alternative to conven- of these feedstocks, their pyrolysis properties should be fully under-
tional fuel products [1,2]. Numerous liquefaction technologies have stood, but it is impractical and time-consuming to analyze the pyrolysis
been applied in biomass conversion to obtain bio-oil, such as fast pyr- properties of each biomass. Thus, it is important to study biomass
olysis, gasification, and Fischer-Tropsch synthesis [3]. Among them, pyrolysis in terms of biomass group components. Indeed, the pyrolysis
fast pyrolysis of biomass is an efficient way for converting biomass into of raw biomass is the sum of its group component pyrolysis, which is
bio-oil with high liquid yield (58–77%) and the bio-oil derived from fast proved by the previous works. For example, lignocellulosic biomass
pyrolysis has advantage of storage, transport, high added value and pyrolysis could be well simulated by its typical components (cellulose,
high calorific value [4–6].Therefore, bio-oil produced through fast Hem and lignin); marine biomass pyrolysis could be well described by
pyrolysis has received much attention in recent years. In industrial the pyrolysis behavior of oil, protein and carbohydrate [9–13]. Hence,
application of biomass fast pyrolysis, according to the pyrolysis prop- the most basic task at present is to extend the basic knowledge on
erties of biomass, it can not only increase the productivity of bio-oil but pyrolysis characteristics of biomass group components, so as to describe
also improve the product quality to choose reasonable fast pyrolysis the pyrolysis of biomass using biomass group components by de-
reactor (such as fluidized bed reactors, ablative pyrolysis reactors and termining its compositions and contents. However, the pyrolysis study
down tube reactors) and process parameters (such as heating rate, of biomass group components is also a great challenge due to the var-
pyrolysis temperature and residence time). This requires us to fully ious origins, forms and complexity of biomass. Facing with such a wide
understand the pyrolysis characteristics of various biomass applied to variety of biomass group components, it is necessary to classify and
fast pyrolysis. summarize the types of biomass group components and form a

⁎
Corresponding author at: State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, China.
E-mail address: Qiao_yingyun@126.com (Y. Qiao).

https://doi.org/10.1016/j.enconman.2020.112777
Received 25 November 2019; Received in revised form 25 March 2020; Accepted 26 March 2020
0196-8904/ © 2020 Elsevier Ltd. All rights reserved.
P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

Nomenclature TG thermogravimetric
Tf terminal devolatilization temperature
A pre-exponential factor Tin initial devolatilization temperature
DTG derivative thermogravimetric Tmax temperature of maximum decomposition rate
Di devolatilization index Rmax maximum decomposition rate
Ea activation energy α conversion rate
FTIR Fourier Transform Infrared β heating rate
Hem hemicellulose

representative classification method of biomass group components for these six components, the pyrolysis of these six components need to be
different types of biomass. Although biomass has a wide variety of studied systematically and deeply. The pyrolysis behavior and kinetic
chemical components due to the various origins or species, its compo- studies of biomass could deepen the comprehension of the pyrolysis
nent type can be divided into a limited number of categories according mechanism to some extent, which are essential for selection, design and
to the similarity of their chemical structure, such as polysaccharide, optimization of reactors [23,25]. For this purpose, thermogravimetric
protein, oil and lignin [7,14]. Obviously, these components with dif- analysis (TG) coupled with FTIR is usually used to investigate the
ferent chemical structure have different pyrolytic characteristics. biomass pyrolysis behavior and kinetics. The kinetic parameters could
Polysaccharides are usually composed of monosaccharides and con- be calculated by the data obtained from TG analysis by using kinetic
nected by glycosidic bonds. The polysaccharides in biomass are mainly models, which were mainly divided into two categories: model-free
Hem, Cellulose (both exist in lignocellulose) and starch (exist in food method and model-fitting method. In this case of model-fitting method,
waste or cereal crop). Hem is a heteropolysaccharide with amorphous reaction mechanisms must be provided to calculate the kinetic para-
and branched structure, and composed of monosaccharides, such as meters, while in model-free method, no reacting mechanisms was pre-
glucose, xylose, arabinose and mannose [11]. It is unstable and easily assumed. As for the pyrolysis of biomass, its real reaction mechanism is
degraded by acid and base, which makes it difficult to extract from extremely complex, and the appropriate reaction mechanism of biomass
biomass. Therefore, xylan, the main component of Hem, is often used in is often difficult to assume. Hence, model-free method, without as-
the study of Hem pyrolysis [15]. Hem is easily pyrolyzed and ap- sumption of reaction mechanism is more suitable for biomass pyrolysis
proximately 70%wt of Hem occurs between 180 and 350 °C [16]. The study [26]. In addition, the characteristic functional groups of gaseous
pyrolytic products on Hem mainly include acids, furans, ketones alde- products from biomass pyrolysis could be identified by the coupled
hydes and anhydrosugars. Cellulose and starch are polysaccharide of FTIR in real time, which is helpful to deepen the understanding of the
glucose, which have high degree of polymerization and crystallinity pyrolysis process. However, it is noteworthy that FTIR coupled with TG
compared with Hem. Starch and cellulose have the same chemical just can identify a type of compounds rather than a certain substance.
formula, but different molecular geometry. Starch is consisted of re- Therefore, the biomass pyrolysis products could not be effectively
peating glucose linked by α-glycosidic bonds, whereas cellulose is identified by TG-FTIR. Fortunately, the technique, Py-GC/MS, can be
comprised of repeating glucose linked by β-glycosidic bonds [17]. The β able to analysis the composition and distribution of volatiles released
-linked bound makes cellulose easier to form crystals, So the crystal- from the biomass pyrolysis accurately. Therefore, the application of
linity of cellulose is generally higher than that of starch, which makes these hyphenated technologies to these six biomass components is
the pyrolysis characteristics of starch and cellulose different. For ex- bound to give a deeper understanding of their pyrolysis mechanism,
ample, the initial temperature of starch is generally lower than that of and the use of these two technologies to investigate the six biomass
cellulose [17]. As the primary source of diverse types of nitrogenous group components is still rare [25].
compounds in bio-oil, protein is composed of amino acids linked by Therefore, the pyrolysis behavior, gaseous product evolution and
peptide bonds [13]. Although there are many kinds of protein in bio- product distributions of the six components (starch, cellulose, Hem,
mass, their pyrolysis properties (such as product type and distribution) lignin, protein and oil) were systematically studied by the hyphenated
are similar because of their similar amino acid structure. For example, technology of TG-FTIR and Py-GC/MS. Then, their kinetic parameters
during the protein pyrolysis, 21%-38% of nitrogen in feedstock is were estimated through Friedman method. The basic data for pyrolysis
transferred to bio-oil, and 36%-62% enters the gas phase as NH3 or HCN behavior, gaseous product evolution, kinetics and products distribution
[18]. Oil is mainly present in oil-rich biomass, such as microalgae, le- based on six biomass components could provide a further insight into
gume and palm shell. The pyrolysis of oil can generate large amount of biomass pyrolysis and provide necessary parameters to predict the
long chain olefins, acids and esters because of its fatty acid moieties pyrolysis behavior of different type biomass in industrial application.
[19]. Triglycerides were the main content of oil in biomass, and the
pyrolysis process can produced nearly 20% cyclic hydrocarbons and
2. Experimental
could be deeply processed into middle-distillate transportation fuels
[20]. Lignin, a phenyl biopolymer consisting of three basic units
2.1. Materials preparation
(namely p-hydroxyphenyl, guaiacyl and syringl units), mainly produces
alcohols, acetic and phenol derivatives during pyrolysis [21]. The pri-
The biomass components studied in this work were classified into
mary decomposition of lignin occurs under a wide range of temperature
six categories, including starch, cellulose, Hem, protein, lignin, and oil.
(200–800 °C) and the pyrolysis reaction rate of lignin is lowest among
According to their chemical structures, these six categories were re-
biomass components because of the more complex and thermally stable
presented by corresponding model compounds. Cellulose was quanti-
structures in lignin [16]. In summary, it is necessary to systematically
tative filter paper (cellulose content > 99.8%) supplied by Hangzhou
study the properties of biomass components due to their different
WoHua filter paper Company, China. Lignin (CAS:9005-53-2) was ac-
pyrolytic characteristics. More specifically, after analyzing a wide range
quired from J＆K Chemicals, China. Hem (represented by xylan) was
of biomass components, biomass components could be divided into six
bought from Sigam-Aldrich (Wuxi) life science＆ technology Co. Ltd,
categories, including starch, cellulose, Hem, protein, lignin, and oil
Jiangsu Province, China. Protein (soy protein) was provided by
[7,11,22–24]. To the best of our knowledge, relatively few literatures
Shanghai Jiaoyuan Co. Ltd, China. Oil (palm oil) and starch (corn
have studied the pyrolysis of these six components simultaneously. In
starch) were collected from Qingdao, Shandong province, China. Before
order to guide the pyrolysis of biomass with different components by
the test, all the samples (starch, cellulose, Hem, lignin, protein) except

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

oil were milled and sieved to the desired particle size less than 75 μm. The kinetic parameters could be calculated from TG curves by using
Then, all the samples were dried in a vacuum-oven at 80 °C for 12 h various methods, which can be classified into two categories (model-
before use. fitting method and model-free method) [31]. Model-free method is
more popular in pyrolysis studies of biomass as it can get more reliable
2.2. Experimental methodology activation energy without assumption of the mechanism function, and
Friedman method, a model-free method, was recognized as the most
Proximate analysis of the six components was evaluated by using accurate one [32]. Therefore, Friedman method was applied to de-
the Chinese National Standards GB/T 212-2008 and ultimate analysis termining the apparent activation energy (Ea) of biomass pyrolysis in
was performed on an elemental analyzer (Vario Macro cube, Elementar this study. Taking the logarithms of both sides of Eq. (2) could obtain
Corp., Germany). Then, their infrared spectrum was measured using a the Friedman-method [33]
Bruker Tensor 27 FTIR spectrometer, which operated at a resolution of d Ea
4 cm−1 in the range of 4000–400 cm−1. Subsequently, their thermo- ln = ln [A·f ( )]
dT RT (3)
gravimetric analysis (TG) was performed in a TG/DTG analyzer
From this equation, for a constant α, Ea could be calculated by
(STA4499 F3, NETZSCH, Germany) coupled with FTIR spectrometer.
plotting ln(β·dα/dT) vs 1/T at various heating rate.
More specifically, sample (5 mg) was heated at various heating rates
(low heating rate (15 °C min−1, 30 °C min−1, 60 °C min−1) and high
3. Results and discussion
heating rate (160 °C min−1)) to 950 °C min−1 under flowing N2 of
100 cm3 min−1. The temperature of the transfer-line (connected be-
3.1. Characterization of six biomass components
tween TG and FTIR) and gas cell was set at 200 °C to avoid volatile
condensation.
The proximate and ultimate analysis of six biomass components is
The experiment of Py-GC/MS was carried out in a CDS 1500 pyr-
shown in Table 1. The volatile content of starch (91.23%), cellulose
olyzer with direct connection to gas chromatography coupled with mass
(96.66%), Hem (90.81%) was very high, and all of them were greater
spectrometry (436-GC/SQ-MS, Bruker, USA). For each run, individual
than 90%, which was basically consistent with the results of previous
component (0.3 mg) was loaded into pyroprobe. The pyroprobe was
literatures (starch-92.77%, cellulose-95.0% and Hem-89.31%) [34,35].
initially set at 280 °C, then heated to 550 °C at a heating rate
Their O/C ratio (0.62, 0.87 and 0.93, respectively) was higher than
10 °C ms−1 and held for 20 s. The operation parameters of GC/MS were
others (protein, lignin and oil), which was attributable to their similar
as follows: DB-5MS column, 60 m × 0.25 mm × 0.25 μm; injector
structure (oxygen-rich polysaccharides) [11,36]. In contrast, oil had the
temperature, 300 °C; flow of Helium, 0.7 mL min−1 with a split ratio of
lowest O/C ratio (0.11) and the volatility of oil was close to 100%
50:1; oven temperature, from 40 °C(held for 3 min) to 180 °C with
whereas that of protein (83.25%) was lower, especially for lignin
3 °C min−1 (held for 3 min), then heat to 280 °C with 4 °C min−1(held
(65.74%). The fixed carbon of the six components was in the order of
for 10 min); EI mode (70 eV) with the m/z ranging from 35 to 450.
lignin > protein > Hem > starch > cellulose > oil. The order
Identification of peak was via the National Institute of Standards and
revealed that lignin and protein were the primary source of biomass
NIST mass spectral library and literature.
char. Among the six components, only protein contained a lot of ni-
trogen (14.9%), which was consistent with the fact that lots of ni-
2.3. Kinetic methods
trogenous matters, such as NH3, HCN, HNCO, N-heterocycles, pyrroles,
and pyridines were released during pyrolysis.
The pyrolysis of biomass could be described by [27–30]
d Ea 3.2. Pyrolysis behaviors of six components
= k (T ) f ( ) = Aexp f( )
dt RT (1)
Pyrolysis behaviors of the six components at various heating rates
where t is the time (min), A is the pre-exponential factor (min−1), Ea is (15 °C min−1, 30 °C min−1, 60 °C min−1160 °C min-1) are shown in
the activation energy (kJ mol−1), R is the ideal gas constant Fig. 1. In the following discussion for the pyrolysis behavior of the six
(8.314 J mol−1 K−1), T is the absolute temperature (K), and f ( ) is the components, 15 °C min−1 was taken as an example. Usually, their
model function in the kinetic equation. The variable α is conversion of pyrolysis behaviors are greatly dependent on their chemical structure.
the sample, = (m 0-m t ) , where mt, m0, and m∞ are the mass of sample
(m -m )
0 Hem was the most easily decomposed among these three poly-
presented at arbitrary, initial and final times respectively. Here, the saccharides (Hem, cellulose and starch), due to its abundant thermally
heating rate β can be defined as = dt , and a new Eq. (2) can be ob-
dT
unstable side branches, such as side linked monosaccharide residues
tained by substituting β into Eq. (1). [37,38]. It decomposed between 203.0 °C and 464.3 °C with the max-
d A Ea imum decomposition rate of 19.67% min−1 at 300.0 °C. Starch and
= exp f( ) cellulose are both comprised of repeating glucose units ([C6H10O5]),
dT RT (2)
while the former linked by α-1, 4-glycosidic bonds and the latter linked

Table 1
Proximate and ultimate analysis (wt.%) of six biomass components.
Sample Proximate analysis Ultimate analysis (daf) H/C O/C

Ma Ad Vdaf FCdaf C H O* N S

Starch 7.42 0.41 91.29 8.71 50.34 8.19 41.46 0.01 0.00 1.95 0.62
Cellulose 4.76 0.05 96.66 3.34 43.44 6.42 50.14 0.00 0.00 1.77 0.87
Hem 4.32 0.12 90.81 9.19 41.76 6.72 51.51 0.01 0.00 1.93 0.93
Lignin 5.33 16.40 65.74 34.26 61.48 5.86 29.55 0.03 3.08 1.14 0.36
Protein 8.78 4.59 83.25 16.75 51.07 7.72 25.19 14.90 1.12 1.81 0.37
Oil 0.06 0.02 100.00 0.00 77.11 11.77 11.09 0.00 0.03 1.83 0.11

*: calculated by difference; daf: dry and ash-free base; Ma: moisture (as received basis); Ad: ash (dry base); Vdaf: volatile matter (dry and ash-free base); FCdaf: fixed
carbon (dry and ash-free base).

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

Fig. 1. TG and DTG curves of six biomass components at different heating rates (the arrow indicates the ordinate of TG and DTG curves).

by β-1, 4-glycosidic bonds. The β-linked way is conducive to the for- 781.3 °C with the decomposition rates of 3.94% min-1 and 1.71%
mation of hydrogen bonding, leading a strong, fibrous nature in cellu- min−1, respectively. The cleavage of side chains between the aromatic
lose [17]. Given the plenty of hydrogen bonds in cellulose, it was easy rings, such as propyl chains and methoxy groups, was responsible for
to understand that cellulose decomposed over a higher temperature the first mass loss. The rupture of the ether linkage 4-O-5 still remaining
range (302.9 °C to 387.8 °C) than that of starch (246.6 °C to 366.5 °C). in the residue at high temperature resulted in the second mass loss,
Protein was mainly composed of amino acid including both aliphatic which was confirmed by the fact that only CO and CO2 were detected in
amino acid and aromatic acids, such as glutamic acid and phenylala- the second mass loss zone as shown in Fig. 4 [40].
nine. It decomposed in the temperature range of 189.1 °C−407.5 °C, As listed in Table 3, the char yield of the six components followed
which was related to decarbonylation and deamination reactions. Oil the order of lignin > protein > Hem > starch > cellulose > oil at
presented a sharp devolatilization process and its initial and maximum the heating rate of 15 °C min−1, which was consistent with the prox-
decomposition temperature were 356.2 °C and 423.5 °C, respectively. imate analysis in Table1. The coking tendency of cellulose and oil was
The pyrolysis temperatures of oil were higher than those of the others. weak but strong for starch, Hem, protein, and especially for lignin.
Generally, oil is mainly composed of triglycerides with long aliphatic Because of plenty of aromatic rings in lignin which will form the char, it
chains. The stable CeC and CeH bonds in the long aliphatic chains is easy to see why lignin has the highest char yield (> 40%). Similarly,
resulted in the high pyrolysis temperature of oil [39]. Because of the aromatics are also present in the side substitutions of amino acids of
various functional groups of lignin with different thermal stability, protein, and these coking precursors such as aromatics make protein
lignin decomposed slowly in a wide temperature range of easy to coking [41]. Although both cellulose and starch are composed
149.0–809.6 °C [16]. Its DTG curve exhibited two peaks at 345.4 °C and of glucose, cellulose is mostly crystalline while starch is amorphous and

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

the amorphous phase is thermally less stable than crystallinity phase Table 2
[17]. Because of the lower stability of amorphous phase, some re- Linear equations of six components with respect to Di and heating rate.
arrangement reactions such as conversion of sugar ring and dehydra- Components Linear equations R2
tion occur in the amorphous phase before the depolymerization takes
place [11]. The rearrangement reactions stabilized the residue and Starch y = 0.2251x + 8.197 0.9561
Cellulose y = 0.1068x + 16.049 0.9762
limited its depolymerization [42]. Hence, starch had a higher coking
Hem y = 0.5173x + 0.0383 0.9971
rate than cellulose. Moreover, this mechanism was applicable to Hem as Lignin y = 0.0339x + 0.2983 0.9996
well, because Hem is only constituted by an amorphous phase in con- Protein y = 0.1142x + 5.560 0.9507
trast to cellulose and starch. In addition, the pentosane existing in Hem Oil y = 0.1952x + 2.878 0.9935
(xylan) is easier to form char than glucan existing in cellulose and
starch because the xylopyranosyl cation formed by xylan is less stable
compared to the glycosyl cation formed by cellulose or starch [43]. The cellulose ≈ protein > lignin. This effect was particularly significant
combination of these two factors leads to the high coking rate of Hem. for Hem. For example, the Di of the six components at the heating rate
As for oil, it had the lowest coking rate (near zero), owing to its simple of 15 °C min−1 were in the order of cellulose (16.69) > starch
chain and aryl-free structure [24]. (9.12) > protein (6.23) > Hem (5.98) > oil(5.13) > lignin (0.45),
In this study, Tin (initial devolatilization temperature), Rmax (max- but as the heating rate increased to160°C min−1, the Di of Hem in-
imum decomposition rate), Tmax (temperature of Rmax) and Tf (terminal creased rapidly, and the Di of the six components followed the new
devolatilization temperature) were applied to describe the pyrolysis order of Hem (82.03) > starch (42.86) > oil (33.75) > cellulose
behaviors of the six components. Specially, Tin and Tf were the tem- (32.77) > protein (23.13) > lignin (4.19). The devolatilization sen-
perature of intersection point of tangent line at the corresponding po- sitivity of each component to heating rate may be related to the acti-
sition of DTG curves. In addition, the devolatilization index (Di) was vation energy, the number of weak bonds and coking precursors
defined to evaluate the release performance of volatiles, which could be [46,47]. For example, the activation energy of Hem is low in the initial
expressed by Eq. (5) [28,44]: reaction stage, as shown in Fig. 6, and the weak bonds of Hem will
rupture in low temperature which is favorable for coking by re-
Rmax arrangement reaction. As the heating rate increased, shortening of re-
Di =
Tin Tmax T1/2 (5) sidence time in low-temperature range prevents rearrangement reac-
where ΔT1/2 is the temperature interval with Rd/Rmax = 0.5. Rd is the tion, but promotes devolatilization process. Hence, low activation
decomposition rate obtained from DTG curves. The values of Di for the energy and large number of unstable bonds make the devolatilization of
six components increased as the heating rates increased, indicating that Hem sensitive to heating rate. In contrast, the high activation energy
the high heating rate enhanced the devolatilization. For example, the Di and coking precursor of lignin resulted in the low devolatilization
for starch was 9.12 at the heating rate of 15 °C min−1 while it was sensitivity to heating rate.
42.86 at the heating rate of 160 °C min−1 in Table3. Generally, the high
heating rate shortened the residence time of components at low tem- 3.3. FTIR analysis of six components
perature and extended that of components at high temperature ac-
cordingly. Moreover, devolatilization reaction is endothermic, while In this work, the six components were characterized by FTIR and the
the formation of char is usually exothermic [45]. Therefore, increasing volatiles of the six components during the pyrolysis at the heating rate
the heating rate promoted devolatilization reaction and inhibited con- of 60 °C min−1 were measured by means of TG-FTIR. As shown in
densation reaction in the view of reaction equilibrium. Meanwhile, this Fig. 3, the FTIR spectra of polysaccharides (starch, cellulose and Hem)
result was also supported by the char yield of the six components. For had a good similarity. The broad band around 3400 cm−1 was related
example, the char yield of lignin was 46.87% at the heating rate of to eOH stretching vibration, and the bands at 2700–3000 cm−1 were
15 °C min−1, while the char yield reduced to 42.29% at 160 °C min−1. ascribed to eCH2 and eCH3 stretching vibration. The peak around
Interestingly, Di of each component had a linear relationship with the 1630 cm−1 was associated with absorbed water, which was also re-
heating rate as shown in Fig. 2 and Table2, and the slope of line could ported in previous literature [48,49]. The peaks located at
reflect the devolatilization sensitivity of each component to heating 800–1200 cm−1 were ascribed to CeOeC stretching vibrations within
rate. The sensitivity followed the order of Hem > starch > oil > saccharide rings, such as 1043 cm−1 (stretching vibration of the gly-
cosidic bond in Hem) and 1161 cm−1 (CeOeC asymmetric valence
vibration in starch and cellulose) [36,37,50]. In addition, the unique
1730 cm−1 (C]O stretching vibration) of Hem implied that it had
acetyl groups, indicating that Hem has many branching structures [51].
It is for the similar polysaccharide structure that the evolved gases of
the three polysaccharides also had similarity. The gas products of these
polysaccharides(starch, cellulose, and Hem) included H2O
(3735 cm−1), CO2 (2359 cm−1, 669 cm−1), CO (2181 cm−1), C]O
(1900–1650 cm−1) and CeO/CeC (1000–1300 cm−1) [49,52]. As
shown in FTIR spectra of lignin, the peaks of 1601 cm−1, 1513 cm−1,
1426 cm−1 were related to aromatic skeletal vibrations [40]. The ab-
sorption peak at 3426 cm−1 was attributed to phenolic and aliphatic
OeH stretching vibration. The peaks at 2934 cm−1, 2852 cm−1 and
1463 cm-1were mainly attributed to the CeH stretching and eCH2
bending vibration in the methyl and methylene groups, respectively,
which related to the propane collateral structure of lignin. The peak
appearing at 1717 cm−1 corresponded to vibration of C]O in non-
conjugated ketone or carbonyl groups, which usually had higher re-
activity activity than conjugated C]O [53]. Several guaiacyl char-
Fig. 2. Devolatilization index (Di) (to evaluate the release performance of vo- acteristic peaks, such as 1267 cm−1 (guaiacyl ring breathing with CeO
latiles) versus heating rate relationship estimated for six components. stretching vibration), 1130 cm−1 (CeH in-plane deformations of

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

Fig. 3. FIIR spectra of the six raw components and their gas products during pyrolysis (60 °C/min) at Tmax.

guaiacyl ring), 860 cm−1 and 818 cm−1 (both ascribed to CeH out-of- to the unique nitrogen-containing structure of protein, the released
plane vibrations of guaiacyl ring) were observed while the peak located gaseous species, such as HCN (3333 cm−1 and 714 cm−1), HNCO
at 1326 cm−1 (CeO stretching vibration of syringyl ring) was not ob- (2251 cm−1), and NH3(966 cm−1), were detected [58]. As shown in the
served, implying that this lignin was mainly composed of guaiacyl units FTIR spectra of oil, oil showed the characteristic absorption of trigly-
[53,54]. During the pyrolysis of lignin, CH4(3016 cm−1) was clearly cerides including C]O of ester stretching vibration at 1741 cm−1,
observed, which was related to the cleavage of the aliphatic side CeOeC (ester) stretching vibration between 1000 cm−1 and
branches and methoxy groups [55]. According to the structure of lignin, 1250 cm−1, and the overlapping of (CH2)n rocking vibration at
the wavenumber region in 1310–1410 cm−1 for lignin was mainly 723 cm−1 [59]. As shown in the FTIR spectra of oil, the absorption
contributed by the C-OH stretching vibration of phenol [30,56]. As intensity of CeH and CH4 was the highest during the pyrolysis of oil
shown in the FTIR spectra of protein, protein exhibited several poly- because of the rupture of long-chain-alkyl in oil. In summary, pyrolysis
peptide characteristic, such as 3080 cm−1 (OeH plus NeH stretching of the six components yielded different kinds of products, which was
vibration), 1656 cm−1 (C]O stretching vibration),1531 cm−1(in-plane closely related to their structures.
bending vibration), and 1241 cm−1(C-N stretching vibration) [57]. Due In order to systematically investigate the devolatilization trends of

6
P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

the six components, the evolution of some gaseous products along with provide more precursors for dehydration reactions. Generally, the for-
functions of temperatures was shown in Fig. 4. According to the Lam- mation of CH4 was mainly related to the random breakage of aliphatic
bert-Beer law, the absorbance intensity of specific wavenumber was side chains, the decomposition of methoxy (eOCH3) and C]C groups,
proportional to its concentration. Hence, changes in absorbance in- and the secondary cracking of volatiles at high temperature [52]. Given
tensity during the entire pyrolysis process could reflect the variation that oil contained a lot of long aliphatic chains and unsaturated double
trend of product concentration. As shown in Fig. 4, H2O was generated bonds, it was easy to understand that the absorption intensity of CH4
in the whole pyrolysis, which was related to dehydration and cross- during the oil pyrolysis process was highest. Similarly, the CH4 ab-
linking reactions. Starch, cellulose, Hem, and oil produced more sorption intensity of protein was also relatively strong, owing to the
quantity of H2O than that of lignin and protein, because the three numerous alkyl side chains of protein [13]. However, the CH4 releasing
polysaccharides and the oil had a lot of hydroxyl groups, which could curve of protein showed two peaks, indicating that the release of CH4

Fig. 4. The evolutions of gaseous product for the six components at 60 °C min−1.

7
P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

during the pyrolysis of protein may be associated to different me- HNCO and HCN was ascribed to the cracking of cyclic amides, such as
chanisms. Below 500 °C, its evolution was mainly related to the clea- 2,5-piperazinedione [61]. However, at high temperature, the formation
vage of aliphatic chain, whereas above 500 °C, it may be associated of HCN was related to the scission of cyano aromatic compounds
with the profound degradation and rearrangement reactions. Although formed at low temperature [62]. As for oil, the largest quantity of CeH
lignin had a poor liquefaction capacity, the CH4 yield was higher than (alkanes) and olefins was produced during the pyrolysis of oil, which
that of polysaccharides (starch, cellulose and Hem), owing to its in- was ascribed to cracking of its unique long alkane structure [63].
stability of propyl chains and methoxy groups(-O-CH3). As an important
deoxygenation route for biomass pyrolysis, the release of CO2 was as- 3.4. Pyrolysis kinetics of six biomass components
cribed to the decarboxylation of carboxyl and ester [30]. The releasing
temperature of CO2 ranged from 200 to 550 °C during the pyrolysis of As we all know, Ea represented the lowest energy required to start a
starch, cellulose, Hem, and protein, while that for oil and lignin was in a chemical reaction. Briefly, samples with lower activation energy mean
broad temperature range (400–800 °C and 200–900 °C, respectively). that their pyrolysis reaction easily occurred at a higher rate, and the
The CO2 releasing curve of oil showed two peaks (460 °C and 510 °C) initial reaction temperature was low [64]. Therefore, the activation
and the first peak was possibly ascribed to the decarboxylation of car- energy distribution along α could reflect the pyrolysis reaction activity
boxyl, and the second may be related to the reformation of ester [24]. of the six components. In order to demonstrate the obtaining process of
Similarly, lignin also had two CO2 peaks (365 °C and 812 °C) with the Ea, Fig. 5 shows the Arrhenius plots of the six components based on
first peak much higher than the second one. The first peak was relevant Friedman method. It can be seen from the high correlation coefficient
to the decarboxylation and the second was related to the deoxygenation (R2 > 95% at every α) that Friedman method has good fitting effects
of oxygenated groups remaining in residues at high temperature [40]. for the six components.
The amount of CO2 during the pyrolysis of the three polysaccharides Then, the Ea distribution on α dependence of the six components
was higher than that of the other components such as lignin and pro- calculated by Friedman method was shown in Fig. 6. From an overall
tein, owing to the high oxygen content in polysaccharides. As another perspective, the Ea of these six components presented obviously dif-
way to deoxygenate, the emission of CO was related to the breakage of ferent variation trend. Except pyrolysis of oil, whose variation trend of
CeOeC and C]O bonds. Dissimilar to the CO2 evolution of the six Ea was basically unchanged, pyrolysis of cellulose, starch, Hem, lignin
components, the evolution curve of all the components displayed only and protein showed a large variation of Ea. At the initial stage of pyr-
one peak and that for lignin only showed in high temperature range olysis (α = 0.1), Ea of these six components was followed order of
(800–900 °C) which was related to cracking of the ether linkage 4-O-5 Oil > Cellulose > Starch > Hem > Protein > lignin, which was
bonds in lignin residue [40]. The releasing of CO for oil was much consistent with the order of Tin value in Table.3. The thermally unstable
higher than that for others, which was most likely attributed to the branching structure, such as monosaccharide in Hem, β-O-4 aryl ether
cracking of C]O in ester. As regards the evolution curves of C]O, they in lignin and free carboxyl in protein may break at this stage [18,64]. As
were mainly produced by the polysaccharides (starch, cellulose and the conversion rate increased, the value of Ea for Hem, lignin and
Hem) and oil. Protein and Lignin produced less C]O containing species protein raised gradually. Among the six components, the structures of
and lignin produced in a wide temperature range. As for protein, the Hem and lignin were branched and complicated. Generally, the more
release of NH3 occurred in the range 260–560 °C, which was ascribable branching structures the components have, the easier they are to form
to the deamination and hydrogenation reactions among char-N, HCN char. For the pyrolysis of Hem, due to lack of free hydroxyl groups, the
and H radicals [60]. HCN was produced in a wide temperature range large branching fragments could not be stabilized by dehydration, and
(300–800 °C) and the similar tendency was found in the previous lit- they would tend to form char through condensation [64]. In the pyr-
erature [58]. In contrast to HCN, HNCO was produced at slightly higher olysis of lignin with a lot of aromatic structures, the free radicals gen-
starting temperatures, which started at almost 310 °C. The formation of erated by aryl ethers is easier to form char through their random

Fig. 5. Arrhenius plots of Friedman methods for the six components.

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

Table 3
Characteristic of TG analysis of six biomass components.
Parameters Starch Cellulose Hem Lignin Protein Oil

o
A Tin( C) 246.6 302.9 203.0 149.0 189.1 356.2
Tmax(oC) 335.3 352.1 300.0 345.4 320.3 423.5
Rmax(% −27.91 −51.6 −19.67 −3.94 −15.47 −33.26
min−1)
Tf (oC) 366.5 387.8 464.3 809.6 407.5 475.4
T2(oC) – – – 781.3 – –
R2(% min−1) – – – −1.71 – –
△T1/2(oC) 37 29 54 170 41 43
Di(−10-6% 9.12 16.69 5.98 0.45 6.23 5.13
min−1 oC–3)
Char yield 14.57 7.36 17.53 46.87 27.06 0.69
(%)

B Tin(oC) 269.5 314.0 214.1 154.2 200.6 376.8

Tmax(oC) 339.2 364.2 306.4 350.2 325.0 434.6
Rmax(% −54.29 −75.71 −45.46 −7.59 −27.28 −62.99
min−1)
Tf (oC) 378.8 402.6 467.1 836.2 420.7 485.5
Fig. 6. Activated energy (Ea) distribution of six biomass components at dif- T2(oC) – – – 806.3 – –
ferent α based on Friedman method. R2(% min−1) – – – −3.22 – –
△T1/2(oC) 42 34 44 181 51 45
Di(-10-6% 14.14 19.47 15.71 0.78 8.20 8.55
condensation [65]. Obviously, at the initial stage of the pyrolysis, the min−1 oC–3)
multiple branching fragments broke down with low Ea, then the con- Char yield 14.37 6.90 16.53 46.06 26.34 0.62
densation reaction led to the increase of Ea [66]. Thus, the Ea dis- (%)

tribution of Hem and lignin gradually increased as conversion rate in- C Tin(oC) 281.3 326.6 222.6 169.3 215.5 387.5
creased. As the only nitrogen- containing component, protein presented Tmax(oC) 352.9 375.4 317.0 364.8 333.3 445.4
Rmax(% −104.3 −130.04 −96.97 −15.75 −54.12 −120.03
a similar Ea distribution trend compared with Hem and lignin, and the
min−1)
difference was that Ea of protein varied slightly in the conversion rate of Tf (oC) 395.6 421.6 471.9 843.7 441.9 498.0
0.2–0.6, indicating that only a main reaction pathway presented in this T2(oC) – – – 811.6 – –
range [67]. The pyrolysis of protein presents three stages. In the initial R2(% min−1) – – – −6.12 – –
stage of protein pyrolysis (< 300 °C), the unstable fragments were △T1/2(oC) 43 45 41 165 54 44
Di(10-6% 24.43 23.57 33.51 1.55 13.95 15.81
pyrolyzed into protein-derived fragments such as, peptidic, trypto- min−1 oC–3)
phanic and prolinic, corresponding to the low Ea [68]. In the second Char yield 13.11 5.81 14.84 44.44 24.81 0.52
pyrolysis stage (300–350 °C), a large number of peptide bonds in pro- (%)
tein were broken and then formed pyridine, pyrrole, indole and other D Tin(oC) 297.3 330.0 230.6 191 221.8 406.3
heterocyclic nitrogen through deamination, dehydration, decarboxyla- Tmax(oC) 373 393.2 323.2 365.8 357.8 450.4
tion reactions, which was confirmed by FTIR analysis (a large number Rmax(% −278.4 −255.1 −269.0 −43.98 −134.0 −290.3
min−1)
of H2O, CO2, NH3 were observed in Fig. 4) [20]. In this stage, the re-
Tf (oC) 437.1 451.5 508.9 878.1 494.3 514.9
action is relatively simple, so Ea of protein pyrolysis was unchanged. In T2(oC) – – – 844.8 – –
the final pyrolysis stage, condensation reaction in protein pyrolysis led R2(% min−1) – – – −15.95 – –
to the increase in Ea. For the pyrolysis of cellulose, it had significantly △T1/2(oC) 57 60 44 150 73 47
different Ea distribution. The Ea of cellulose decreased gradually Di(10-6% 42.86 32.77 82.03 4.19 23.13 33.75
min−1 oC–3)
throughout the whole pyrolysis, which was similar to previous litera-
Char yield 10.42 4.59 10.96 42.29 22.87 0.21
tures [69]. This phenomenon is mainly attributed to its high molecular (%)
weight and crystallinity [11]. According to the Broido-Shafizadeh ki-
netic model, cellulose was pyrolyzed to the mediate product named Note: A: 15 °C min−1; B:30 °C min−1; C :60 °C min−1; D:160 °C min−1; T2
active cellulose at the initial stage due to its high crystallinity, leading Temperature of the second DTG peak. R2 Decomposition rate of the second DTG
to the reduction of degree of molecular polymerization and crystal- peak.
linity. During the pyrolysis, the formation of active cellulose required a
high barrier while the scission of active cellulose needed a lower en- decreasing Ea. Generally, amorphous region has worse thermal stability
ergy, and the formation of active cellulose could accelerate the cracking than crystalline region, and the amorphous region was prone to parallel
reaction [66]. Additionally, due to the simple chemical structure, the condensation reaction [11]. As starch has more amorphous region than
coking reaction for cellulose was less, which was confirmed by the very cellulose, the parallel condensation reaction for starch cannot be ne-
low char yield in cellulose pyrolysis. Thus, Ea of cellulose reduced glected [17]. So, Ea of starch gradually increased because of con-
gradually with the α increased. As for the pyrolysis starch, an ac- densation reaction in the third pyrolysis stage, corresponding to the
celerated process with decreasing Ea similar to cellulose also occurred. high char yield in TG analysis. Compared to the other five components,
The similar varied pattern of Ea was also reported by previous literature oil has the relatively simple structure, glycerol ester bond, and there
[70]. The pyrolysis of starch could divided into three stages. Initially, a was almost no condensation reaction during the pyrolysis. Thus, the Ea
small amount of loose branched linear structures especially in amor- of oil was basically the same during the entire pyrolysis, indicating that
phous, started to degrade with low Ea and the Ea increased as the re- the main reaction pathway kept the same in the whole process. A
action went on [11]. After the weaker bonds in starch broken down, the previous study have proven that free-radical chain reaction was the
long linear segments, composed of the principal parts of starch, began main reaction pathway in the whole pyrolysis [63]. In order to avoid
to degrade. Because starch and cellulose have similar chemical unit the errors of Ea at low or high conversion rates, the average Ea was
(glucose) and linked bond (glucosidic bond), starch also underwent an discussed at the conversion rates from 0.2 to 0.7 [71]. The average Ea of
acceleration stage similar to active cellulose, which presented a the six components calculated at the conversion rates from 0.2 to 0.7

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

displayed the order of oil > lignin > starch ≈ Hem ≈ protein > from the six components easily, it is necessary to classify their products
cellulose, which showed that the pyrolysis of oil and lignin required based on their chemical structures. As shown in Fig. 7, the main pyr-
higher energy than that of starch, Hem, protein and cellulose in the olysis products of starch, cellulose and Hem were similar. For example,
main reaction stage. they all have large amounts of hydroxy acetaldehydes, furan deriva-
tives, and L-glucose derivatives. Hence, their pyrolysis products could
be divided into similar categories, including carbonyls (aldehydes, ke-
3.5. Py-GC/MS analysis for the six components
tones, acids and esters), O-species (alcohols and ethers), other O-het-
erocycles (furans and sugars), hydrocarbons and others. On the con-
To comprehensively investigate the composition and distribution of
trary, the volatile products from lignin, protein and oil were obviously
pyrolysis products of the six components, the Py-GC/MS was used to
dissimilar. Specifically, lignin mainly produced phenols, such as
analyze the pyrolysis products qualitatively and quantitatively. Fig. 7
phenol,2-methoxy-, and its volatiles products could be divided into
displays the pyrograms of the six components at 550 °C with the heating
phenols (guaiacyls, p-hydroxyphenyls, catechol phenols and syringyls),
rate of 1 °C ms-1 and all detected products were listed in Table S1–S6 of
carbonyls (ketones, acids and esters), alcohols, aromatics and others.
Supplementary material. To analyze the pyrolysis products obtained

Fig. 7. Total ion chromatogram of the six components at 550 °C with the heating rate of 1 °C ms−1.

10
P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

Protein mainly produced nitrogen-containing compounds, such as respectively) while that for Hem was in the range of C5-C6(up to
pyrrole and indole and its volatiles products could be divided into six 22.41%). This indicated that hexoses, such as starch and cellulose were
categories, such as N-species (N-heterocycles, pyrroles, pyridines, ni- more likely to form low carbonyl compounds compared with the pen-
triles and amines), carbonyls (aldehydes, ketones and acids), phenols, toses like Hem. As shown in Fig. 8(d), it was worth noting that starch,
aromatics, hydrocarbons and others. Oil, a compound with a long chain cellulose and Hem all produced large numbers of O-heterocycles in-
structure, mainly produced large numbers of alkenes, and its volatiles cluding dehydrated sugars and furan derivatives, which were up to
products were divided into alkene (monoolefines, dialkenes and cy- 27.6%, 26.48% and 36.56%, respectively, indicating that Hem was
cloalkenes), carbonyls (aldehydes, ketones, acids and esters), alkanes, more likely to undergo the reactions of breaking of glycoside bonds to
alcohols and others. Besides, the relative content distributions and form O-heterocycles. Among O-heterocycles, furan derivatives were an
carbon number distributions of the six component pyrolysis products important chemical raw material and the yield of furan derivatives was
were shown in Fig. 8, which were evaluated by the normalization in the order of Starch(17.68%) ≈ Hem(17.5%) > cellulose(14.21%).
method of peak area. The results indicated that the polysaccharides with lower crystallinity
In detail, for the pyrolysis of starch, cellulose and Hem, the de- or containing pentoses had higher selectivity for furan derivatives,
composition reactions mainly included breaking of glycoside bonds, which was confirmed by previous studies [42].
dehydration, ring scission and rearrangement [13]. Because of their For lignin pyrolysis, phenols were the main products up to 81.4%
similar polysaccharide structure and reaction pathways, their content and the content of guaiacyls, p-hydroxyphenyls, catechol phenols and
distributions and carbon number distributions showed a similar trend. syringyls was 54.92%, 11.14%, 8.71% and 6.68%, respectively.
For example, as shown in Fig. 8 (a), the relative content of oxy-com- Guaiacyls, p-hydroxyphenyls and syringyls were mainly came from the
pounds from starch, cellulose and Hem were in the order of carbo- pyrolysis of guaiacyl, syringyl, and p-hydroxyphenyl units in the ori-
nyls > O-heterocycles > O-species. Moreover, the carbonyl com- ginal lignin structure, which produced by the breaking of abundant
pounds were quite large, which were up to 53.83%, 58.53% and ether linkages, such as β-O-4 [11]. The FTIR of lignin indicated the
43.81%, respectively, indicating that carbonyls were their predominate lignin in this study contained primarily guaiacyl unites, so guaiacyls
products, which was confirmed by TG-FTIR. Furthermore, as depicted became the main product through the direct breaking of β -O-4 bond
in Fig. 8(c), the carbon number range of their pyrolysis products were while syringyl was rare in the volatiles. P-hydroxyphenyls, catechol
mainly in the range of C1-C10, and reached the maximum at C5-C6 phenols are mainly formed at high temperatures (600–700 °C), so their
(mainly derivatives of furan and dehydrated sugar), which were pro- content was also rare [53]. The high content of phenols for lignin lead
duced by the reactions of breaking of glycoside bonds and ring scission to its carbon number distribution mainly in C7-C10, and up to 77.20%.
[11]. Although the types of their pyrolysis products were similar, their For protein pyrolysis, it mainly produced a large number of N-species
specific products are slightly different. As depicted in Fig. 8(d), the up to 52.71% because of higher nitrogen element content in protein.
carbon number distribution of carbonyls for starch and cellulose The content of N-heterocycles, pyrroles, pyridines, nitriles, amines/
reached the maximum at C2-C4(up to 35.50% and 36.39%, amides were 19.83%, 5.61%, 4.75%, 12.74%, and 9.78%, respectively.

Fig. 8. The distributions of pyrolysis products and Carbon number for the six components.

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P. Zong, et al. Energy Conversion and Management 216 (2020) 112777

The cyclic nitrogen-containing compounds, such as N-heterocycles, study, because their pyrolysis properties were obviously different, which
pyrroles and pyridines mainly came from the cyclization reaction of had great significance for understanding the pyrolysis of biomass con-
amino acids, as it had eCOOH and eNH2 groups, which form cyclic taining these components. From the order of devolatilization sensitivity to
nitrogen compound by dehydration cyclization [68]. Specially, protein heating rate (Hem > starch > oil > cellulose ≈ protein > lignin.),
was also a source of phenols compared with lignin and this was mainly high heating rate promoted devolatilization for biomass rich in Hem and
due to the pyrolysis of amino acids with phenolic substances, such as starch, but not for biomass rich in lignin. The average activation energy of
tyrosine [72]. Different from the other five components, oil produced each component calculated by Friedman methods was in the order of in
large amounts of alkenes (46.48%), mainly including monoolefines the order of oil > lignin > starch ≈ Hem ≈ protein > cellulose, in-
(34.82%), cycloalkenes (6.01%), and dialkenes (5.65%). These alkenes dicating that biomass rich in starch, oil and lignin was difficult to pyrolyze,
mainly came from the cracking reactions and decarboxylation reactions while biomass rich in starch, cellulose, protein and Hem was easy to
of the long-chain structure in triglycerides [73]. Specifically, it can be pyrolyze. Starch and cellulose were more likely to form low carbon
seen form Fig. 7, a large number of shorter-chain alkenes, such as number carbonyl compounds (C2-C4) compared with Hem(C5-C6), while
propene, 2-pentetene, 1-hexene and 1-hepene were produced from the starch and Hem had higher selectivity for furan derivatives. Lignin mainly
oil pyrolysis, which were mainly produced by the β -scission reaction produced phenols (up to 81.4%), among which guaia-
[24]. These shorter-chain alkene could potentially be used as sub- cyls accounted for 54.92%. Protein produced a large number of N-species
stitutes for petrochemical products and had tremendous value. In ad- up to 52.71%, mainly including N-heterocycles (19.83%), pyrroles
dition, a large number of carbonyl compounds (42.05%) including acids (5.61%), pyridines (4.75%), nitriles (12.74%) and amines/amides
(30.05%), eaters (4.33%), aldehydes (4.24%) and ketones (3.43%) (9.78%). The oil-rich biomass was a potential material for the production
were obtained from the pyrolysis of oil. As shown in Fig. 7, a large of high-value low-carbon olefins, which produced large amounts of al-
amount of acids, such as n-hexadecanoic acid, was produced from the kenes (46.48%) by the oil pyrolysis.
oil pyrolysis. This may be that a large number of carboxylic acids The following study will focus on the co-pyrolysis of these six bio-
contained in oil has not reached the temperature of decarboxylation mass components to better understand the pyrolysis of various biomass
before it was carried into the GC/MS by the carrier gas [24]. As proof, it species, such as co-pyrolysis of polysaccharide and protein, co-pyrolysis
can be seen from Fig. 8 (d) that the carbon number of carbonyls was of protein and oil, co-pyrolysis of lignin and oil, etc. Simultaneously,
mainly in the range of C16-C18, which was the common carbon dis- the verification experiments to explain biomass pyrolysis using these six
tribution of fatty acids in oil [74]. Therefore, given sufficient reaction components was also worth conducting in future.
time, this large amount of fatty acids could be converted to shorter-
chain alkene to generate high value. CRediT authorship contribution statement
To better understand the pyrolysis of various biomass species, the
possible pyrolysis pathway of these six components were proposed Peijie Zong developed the original structure of the draft. Yuanyu
based on TG-FTIR and Py-GC/MS analysis. As for the pyrolysis of cel- Tian, Dawei Li and Yuan Jiang revised the manuscript by substantially
lulose, Starch, and Hem, their pyrolytic pathway were similar due to restructuring it and adding up critical insights. Yaoyao Ji, Li Jie,
the similar polysaccharide structure. Their pyrolytic path followed two Menshen Chen and Meng yuan reviewed and edited this manuscript.
competing pathways: break of glycoside bonds to form anhydrous sugar Yingyun Qiao is the corresponding authors who communicate on behalf
and ring breaking of light oxygenated compounds [75]. The difference of all authors. We further confirm that all authors have checked the
was that starch and cellulose went through an accelerated process manuscript and have agreed to the submission.
named active cellulose, while Hem did not [11]. For lignin pyrolysis,
the pyrolytic path followed the free radical mechanism [65]. There are Declaration of Competing Interest
two competitive routs: the cleavage of to β-O-4 to form phenolic deri-
vative and the polymerization of radicals produced by hemolysis of aryl The authors declare that they have no known competing financial
ethers to form char. These made the Ea of lignin pyrolysis gradually interests or personal relationships that could have appeared to influ-
increased in pyrolysis process. As For pyrolysis of protein, the break of ence the work reported in this paper.
peptide bonds tended to form free amino acids, and then the amino
acids generated cyano-N, heterocyclic-N and amine-N, through dea- Acknowledgements
mination, dehydration and decarboxylation reactions, which was con-
firmed by the releasing of NH3, H2O and HCN in TG-FTIR analysis [13]. This work was supported by the National Natural Science
The cyclization of amino acids is the dominant reaction, producing a Foundation of China (Grant Nos. 21576294 and 21706287), the
large number of N-species (up to 52.71% in this study), corresponding Taishan Scholar Foundation of Young Expert (tsqn201812028), the CAS
to the constant Ea of protein pyrolysis in this stage (α = 0.2–0.6). Key Laboratory of Carbon Materials (KLCMKFJJ2013), the Qingdao
Gallois studied 20 protein amino acids and proposed the pyrolysis path, Municipal Science and Technology Bureau (16-6-2-51-nsh and 18-6-1-
which was suitable for describing the protein pyrolysis path [76]. For 101-nsh) and the Fundamental Research Funds for the Central
the possible pathway of oil, the triglycerides were first cleaved to Universities (18CX05022A).
generate fatty acids, and then tend to form hydrocarbons and oxyge-
nates by decarboxylation reaction, which was proved by the TG-FTIR Appendix A. Supplementary data
analysis that CO2 was the first released gas (at 350 °C) [24]. Then
pyrolysis of long-chain hydrocarbons and fatty acids followed the me- Supplementary data to this article can be found online at https://
chanism of free-radical chain reaction, which kept the pyrolysis of Ea doi.org/10.1016/j.enconman.2020.112777.
basically unchanged in the whole process [63]. The cleavage of CeC
bond in chain reaction through β -scission tend to form a large number References
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