Energy Conversion and Management 120 (2016) 370–377

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Thermal degradation of beech wood with thermogravimetry/Fourier

transform infrared analysis
Yanming Ding a,b, Ofodike A. Ezekoye b, Shouxiang Lu a,⇑, Changjian Wang c,⇑
a
State Key Laboratory of Fire Science, University of Science and Technology of China, Heifei 230027, China
b
Department of Mechanical Engineering, University of Texas at Austin, Austin, TX 78712, USA
c
School of Civil Engineering, Hefei University of Technology, Hefei 230009, China

a r t i c l e i n f o a b s t r a c t

Article history: Pyrolysis of beech wood (Fagus sylvatica) was investigated based on thermogravimetric analysis coupled
Received 7 March 2016 with Fourier transform infrared spectrometry analysis at heating rates from 20 K/min to 60 K/min. The
Received in revised form 29 April 2016 various activation energies were estimated at different conversions by three model-free methods and
Accepted 1 May 2016
were in the range of 146.84–174.44 kJ/mol. The peak locations of three main components (hemicellulose,
Available online 7 May 2016
cellulose and lignin) were predicted more exactly by the K-K method. The absorbance spectra corre-
sponding to the three peak locations were basically the same at different heating rates, indicating that
Keywords:
the heating rate had little influence on the produced composition. During the whole pyrolysis process,
Beech wood
Pyrolysis
the evolution of gas components (CO, CO2, methane, methanol and formaldehyde) was consistent with
Kinetics the trend of derivative thermogravimetric curves, and possible formation pathways of main gases were
Thermogravimetry tentatively presented. The amount of these five components produced in the order of most to least pro-
Gas evolution duced was formaldehyde > CO2 or methanol > methane > CO. In particular, the amount of formaldehyde
was almost triple the amount of methanol and ten times the amount of methane at the maximum peak.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction obtaining weight loss to study biomass thermal decomposition

Increasingly, biomass is seen as an alternative and renewable
energy source [1] with the depletion of fossil fuel and concerns
about environmental protection [2]. Plant biomass, a composite
material mainly comprised of hemicellulose, cellulose and lignin,
is an ideal renewable resource for the generation of heat and power
via thermochemical processes [3]. Beech wood is a typical and
common hardwood, native to temperate Europe, Asia and North
America, that is used for furniture, tools and small household arti-
cles [4]. Due to its mechanical and physical properties, it is one of
the most commonly used wood species in different industrial sec-
tors [5]. In our study, the thermal chemical processes of beech
wood, which are widely regarded as promising methods for utiliza-
tion of biomass [6] are examined.
Pyrolysis is one of the key thermal chemical conversion tech-
nologies [7]. As the first step in the thermal chemical conversion
of biomass materials, it is a thermal degradation of organic matrix
to obtain an array of solid, liquid and gas products in an inert envi-
ronment [8]. Thermogravimetric (TG) analysis coupled with Four-
ier transform infrared (FTIR) analysis is an effective method for
⇑ Corresponding authors.
E-mail addresses: sxlu@ustc.edu.cn (S. Lu), chjwang@ustc.edu.cn (C. Wang).
characteristics, reaction mechanisms and evolved products during
pyrolysis [9]. This method offers the potential for the non-
destructive, simultaneous, real-time measurement of multiple
gas phase compounds in complex mixtures. Mass loss rates and
chemical kinetic parameters can be obtained by TG without the
complex chemical reactions in the thermal degradation, and the
evolved gases are detected in real-time by FTIR [9], which is an
important and often a difficult task in many thermal applications
[10].
For the pyrolysis activation energy of beech wood, Grønli et al.
[11] measured the thermogravimetric curve at a heating rate of
5 K/min, establishing a devolatilization mechanism which con-
sisted of three parallel reactions (corresponding to hemicellulose,
cellulose and lignin) and estimating the activation energy. Branca
and Di Blasi [12] conducted the thermogravimetric experiments
to establish the activation energy from 5 K/min to 40 K/min. Ding
et al. [4] applied the Shuffled Complex Evolution optimization
algorithm to estimate the chemical kinetic parameters. It is noted
that the activation energies in all the above research are obtained
by model-fitting methods, which consist of fitting different models
to the experimental data for the best statistical fit. However, these
methods suffer from several problems, such as the inability to
determine the reaction model and the various kinetic parameters

http://dx.doi.org/10.1016/j.enconman.2016.05.007
0196-8904/Ó 2016 Elsevier Ltd. All rights reserved.
 Y. Ding et al. / Energy Conversion and Management 120 (2016) 370–377 371

with chosen reaction order [13]. Therefore, the isoconversional where m0, mt and m1 are the mass of sample at the initial time, an
method also called model-free method is widely used for estimat- intermedia time t and the end time, respectively. A is the pre-
ing the activation energy at specific extent of conversion for an exponential factor, Ea is the activation energy and n is the reaction
independent model, because it is simple and avoids errors con- order. R is the universal gas constant, and T is the reaction temper-
nected with the choice of a kinetic model [13]. For example, Biagini ature (K).
et al. [14] studied the pyrolysis characteristics of beech wood Substitution of Eqs. (3) and (4) into Eq. (1) gives the reaction
based on various activation energies by the Friedman method rate expression in the form:
(a kind of model-free method) and developed a VEB model. In

da Ea
our study, the common model-free methods including Flynn– ¼ Að1  aÞn exp ð5Þ
dt RT
Wall–Ozawa method (developed by Flynn and Wall [15], as well
as Ozawa [16]), Kissinger–Akahira–Sunose method (developed by For a linear heating rate, b = dT/dt, Eq. (5) can be written as:
Kissinger [17], Akahira and Sunose [18]) and recently proposed

da A Ea
K-K method [19], are applied to estimate the various activation ¼ ð1  aÞn exp ð6Þ
energy at different conversion rates. dT b RT
For the gases evolved during pyrolysis, Pouwels et al. [20] ana- Based on the above equations, three common model-free meth-
lyzed the total beech wood and three derived fractions by pyroly- ods [13] are used to estimate the activation energy of beech wood
sis–gas chromatography–mass spectrometry (Py-GC–MS), listing in this work, including the Flynn–Wall–Ozawa method, Kissinger–
the possible pyrolysis products in 1987. Similarly, the fast pyrolysis Akahira–Sunose method and K-K method. These methods are used
products of beech wood were researched by Greenhalf et al. [21] to obtain the activation energy of a solid state reaction without
compared with straw and perennial grasses by Py-GC–MS. Wester- prior knowledge of the reaction mechanisms [13]. Therein, the
hof et al. [22] studied the effect of particle geometry and Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose integral meth-
microstructure on fast pyrolysis of beech wood in a fluidized bed ods involve measuring the temperatures corresponding to fixed
reactor at 500 °C, especially on char, gas, and pyrolysis oil yield conversion rates from experiments at different heating rates [26],
and pyrolysis oil composition. Moreover, Gorbacheva et al. [5] but according to different approximations [27]. The main advan-
and Tjeerdsma and Militz [23] conducted the FTIR analysis of ther- tage of the K-K method is the application of the absolute second
mally treated beech wood. derivative of mt/m0 to estimate the peak locations, which are very
However, there are not many studies investigating the pyroly- important in the subsequent FTIR analysis.
sis of beech wood using a coupled TG-FTIR technique. The chem-
ical reaction kinetics by model-free methods, product analysis and 2.1. Flynn–Wall–Ozawa method (FWO)
detailed studies on distribution of specific products corresponding
temperature region(s) or mass loss stage(s) by FTIR are relatively The FWO method was developed by Flynn and Wall [15], as well
few [24]. To further improve the understanding of the mechanism as Ozawa [16], based on Doyle’s approximation [28]. This method
of beech wood pyrolysis and the formation of its main products, does not require any assumption concerning the reaction mecha-
this study focuses on thermogravimetric analysis on various heat- nism, other than the Arrhenius type temperature dependence.
ing rates (20–60 K/min), the estimation of chemical kinetic The reaction rate in logarithmic form can be expressed as:
parameters by multiple model-free methods, the gases evolved


during the whole pyrolysis process based on FTIR analysis, and AEa Ea
ln b ¼ ln  5:331  1:052 ð7Þ
the change of gas distribution under different heating rates. RgðaÞ RT
Specifically, the kinetic parameters and detailed distribution of where g(a) is the integral function of conversion:
produced gas obtained in the study can be helpful to couple pyrol- Ra RT ðERTa Þ
ysis model and combustion model for future computational fluid gðaÞ ¼ da
0 f ðaÞ
¼ A
b T0
exp dT. The plot of ln b versus 1/T gives a
dynamics. straight line whose slope can be used to determine the activation
energy Ea. The value of pre-exponential factor A can be obtained
2. Kinetic method analysis from the intercept when g(a) is known.

TG provides a controllable atmosphere and heating rate, with 2.2. Kissinger–Akahira–Sunose method (KAS)
negligible thermal gradients and transport effects during degrada-
tion of small solid samples [25]. The application of TG analysis is The KAS method was developed by Kissinger [17], Akahira and
appropriate to obtain chemical kinetic parameters, such as activa- Sunose [18]. It is similar to the FWO method, requiring the temper-
tion energy. The decomposition rate of solid materials can be mod- ature values at which an equivalent conversion rate occurs for
eled as: various heating rates [29]. This method is based on the following
expression:
da

¼ kf ðaÞ ð1Þ b AEa Ea
dt ln ¼ ln  ð8Þ
T2 RgðaÞ RT
where a is the conversion rate, namely the fraction of solid material
decomposed at time t, k is defined as the rate constant of the Arrhe- A straight line can be obtained with a given conversion rate,
nius reaction equation, and f(a) is the reaction model function. plotting the ln (b/T2) against 1/T, then the activation energy Ea
Usually, the above three parameters can be expressed as follows: would be determined by the slope. Moreover, the pre-
m0  mt exponential factor A also can be estimated by the intercept when
a¼ ð2Þ g(a) is known.
m0  m1

 2.3. K-K method
Ea
k ¼ A exp ð3Þ
RT
The K-K method was recently developed by Li et al. [19],
based on Kissinger method [30]. Biomass materials are mainly
f ðaÞ ¼ ð1  aÞn ð4Þ
composed of three components (hemicellulose, cellulose and
372 Y. Ding et al. / Energy Conversion and Management 120 (2016) 370–377

lignin), and these three components should correspond to three TG furnace. FTIR analysis was conducted with a purge flow of
peaks. Then it makes sense to compute the corresponding activa- 50 mL/min pure helium at two heating rates (20 and 60 K/min).
tion energies once the peak locations are determined. This method The spectrum scan frequency was 20 times per minute with a spec-
applies the absolute second derivative of mt/m0 (|DDTG|) to esti- trum region from 450 cm1 to 4000 cm1 [33]. A transfer line was
mate the peak locations: employed to connect the FTIR to the TG analyzer, and this line was
    heated and maintained at 200 °C to prevent the condensation of
d2 ðm =m Þ X N
d ai 
2
 t 0   the volatile gases evolved during the pyrolysis process.
jDDTGj ¼   ¼  f P0 ð9Þ
 dT
2   i¼1 i dT 2 

where fi = mi,0/m0 is the initial mass fraction of component i and N is
P
the number of components ( Ni¼1 f i ¼ 1). When a major component
is near the maximum decomposition rate, the absolute value of its
second derivative will exponentially drop to zero. So if there is no
disturbance from other major peaks nearby, the value of |DDTG| is
very likely to drop rapidly to a local minimum (LM) [19]. Based
on the established minimum value, the peak locations of major
components are determined. Eventually, the activation energy can
be obtained corresponding to different peaks by the Kissinger
method:
!

b AR Ea
ln ¼ ln  ð10Þ
T 2p;i Ea RT p;i
where subscript p denotes the peak location of different compo-
nent. Similarly, the activation energy can be obtained by the slope
of plot, ln (b/Tp,i2) against 1/Tp,i.
3. Experimental setup
3.1. Sample preparation
The beech wood used in this work was Fagus sylvatica from
Germany. The samples were milled to less than 0.2 mm, avoiding
the temperature gradient within the particles during the measure-
ments. Before the experiment, all the materials were dried at 80 °C
4. Results and discussion
4.1. Thermogravimetric analysis
The effect of heating rate on mass loss rate (DTG) of beech wood
pyrolysis is shown in Fig. 1a. Approximately at 500 K, beech wood
starts to pyrolysis. The shoulder appears between 570 K and 620 K,
while the maximum value of mass loss rate is between 640 K and
670 K. Meanwhile, the shoulder and peak move to higher temper-
atures as the heating rate increases. Then the mass loss rate
decreases rapidly until 700 K. Subsequently, the mass loss rate
begins a slow decline, and eventually its value is close to zero at
800 K. The average value of final residue is about 14% of all the
TG experiments. In total, the mass lost in 500–700 K comprises
as much as 90% of total mass loss. Moreover, based on the DTG
curves for pyrolysis at various heating rates, it indicates that
although heating rate affects the peak value and location of mass
loss rate, it has little impact on the variation tendency of the pyrol-
ysis. Fig. 1b shows the change of conversion rate with temperature
at different heating rates.
12
(a) 20 K/min
10
40 K/min
60 K/min
d (m/m0) /dT×10-3 (K-1)

8
for about 24 h. Vario EL cube by Germany Elementar was employed
for elemental analysis. Table 1 shows the results of elemental,
proximate and biochemical analysis on weight percent in dry basis. 6

3.2. Thermogravimetry 4

The thermogravimetric experiment was conducted on a TA

2
Instrument SDT Q600 thermal analyzer from 300 K to 1000 K with
three heating rates (20, 40 and 60 K/min). A powdery sample with
about 6 mg was evenly distributed in an Alumina cup without a lid 0
400 500 600 700 800 900
for all the experimental runs, and a purge flow of 100 mL/min pure
Temperature (K)
nitrogen was applied to the system during the whole process. The
flow rate was high enough to sweep the produced gas away from 100
the sample to keep the nitrogen atmosphere around it.
(b)
3.3. Fourier transform infrared technique 80 20 K/min
40 K/min
Conversion rate (%)

60 K/min
A Fourier transform infrared (FTIR) spectrometer (PerkinElmer
60
Frontier, USA) was used to character the gases evolved from the

Table 1 40
Elemental, proximate and biochemical analysis of beech wood (% mass, dry basis).

Elemental Proximate analysisb Biochemical analysisc

20
analysis
C 45.52 Ash 0.5 Hemicellulose 28.3
H 6.34 Volatiles 85.7 Cellulose 41.2
0
N 0.16 Fixed carbon 13.9 Lignin 22.2 400 500 600 700 800 900
Oa 47.98
Temperature (K)
a
Oxygen content was obtained by difference.
b
Information from Telmo et al. [31]. Fig. 1. Pyrolytic decomposition at different heating rates: (a) DTG, (b) conversion
c
Information from de Wild et al. [32]. rate.
 Y. Ding et al. / Energy Conversion and Management 120 (2016) 370–377 373

4.2. Kinetics of thermal decomposition -8.4

α=0.1
-8.6
The chemical reaction kinetic parameters, especially the activa- α=0.2
α=0.3
tion energy, are estimated by the results obtained from thermo- -8.8
α=0.4
gravimetric analysis. Three model-free methods described in α=0.5
-9.0 α=0.6
Section 2 are applied during the calculation.
α=0.7
In the first two methods, the conversion rate is chosen between

ln(β/Τ2)
-9.2 α=0.8
0.1 and 0.9 at three heating rates (20, 40 and 60 K/min). According α=0.9
-9.4
to Eqs. (7) and (8), FWO plots (ln b versus 1000/T) and KAS plots
(ln (b/T2) versus 1000/T) are shown in Figs. 2 and 3, respectively. -9.6
Based on the slopes (1.052Ea/R for FWO and Ea/R for KAS), -9.8
various activation energy values are obtained at progressive
conversion rates [34]. Assuming that the reaction order is 1, the -10.0
reaction mechanism functions are then f ðaÞ ¼ 1  a and -10.2
gðaÞ ¼  lnð1  aÞ. Based on the intercept (ln (AEa/Rg(a))  5.331 1.40 1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90
for FWO and ln (AEa/Rg(a)) for KAS), various pre-exponential 1000/T (K-1)
factors are also estimated, as listed in Table 2.
The activation energy is about 148.63–174.44 kJ/mol and Fig. 3. KAS plots for different conversion rates.

146.84–172.21 kJ/mol for the FWO and KAS models, respectively.

The distribution of activation energies is basically the same for Table 2
these two methods with less than 2% deviation, which is caused Calculation results of activation energy (Ea) and pre-exponential factors (A) by the
by the different approximations used in the algorithms [27]. The FWO and KAS methods.
activation energy gradually increases with conversion rate in the a (%) Flynn–Wall–Ozawa Kissinger–Akahira–Sunose
range from 10% to 50%, and then remains about the same from
Ea (kJ/mol) R2 ln A (s1) Ea (kJ/mol) R2 ln A (s1)
60% to 80%, eventually rising again at 90%, as shown in Fig. 4. It
is noted that different activation energy values are associated with 10 148.63 0.99 29.87 146.84 0.99 9.86
20 155.61 0.99 30.95 153.85 0.99 10.88
the reaction rate and the difficulty of a reaction starting [27]. So the
30 162.86 0.99 31.96 161.19 0.99 11.82
fluctuation of the activation energy on the conversion rate can be 40 168.17 0.99 32.53 166.52 0.99 12.35
attributed to the different reactions, namely the reactions of three 50 171.04 0.99 32.68 169.32 0.99 12.45
major components (hemicellulose, cellulose and lignin) in the 60 169.19 0.99 32.03 167.20 0.99 11.78
sample. 70 169.20 0.99 31.86 167.06 0.99 11.57
80 167.45 0.99 31.40 165.07 0.99 11.09
For the third method (K-K), three peaks locations corresponding 90 174.44 0.99 32.41 172.21 0.99 12.06
three major components should be established, and then |DDTG| is
Mean value 165.18 31.74 163.25 11.54
shown in Fig. 5a. Three local minima (LM) appear at 610 K, 666 K
and 719 K, respectively, and Fig. 5b shows the corresponding loca-
tions on the curve of DTG at 60 K/min.
180
Grønli et al. [11] reported that hemicellulose decomposition
should be mainly responsible for the shoulder region of the mass 175 FWO
loss rate curve, cellulose decomposition was associated with the KAS
maximum mass loss rate, followed by a rapid decay and a long tail, 170
and lignin decomposition was slow and occurred over a wide tem-
perature range [4]. Yang et al. [35] indicated that in terms of ther- 165
E a (kJ/mol)

mal degradation, the three major components of biomass in the

160
order of the easiest to the most difficult to degrade were hemicel-
lulose > cellulose > lignin. Tsamba et al. [36] emphasized that the 155
lignin started decomposing at low temperatures (160–170 °C)
150

145
4.4
α=0.1
α=0.2 140
4.2 0 10 20 30 40 50 60 70 80 90 100
α=0.3
α=0.4 Conversion rate α (%)
4.0 α=0.5
α=0.6 Fig. 4. Activation energy (Ea) distribution at different conversion rates (a).
3.8 α=0.7
α=0.8
α=0.9
lnβ

3.6
and continued to decompose at low rate until approximately
3.4
900 °C, hemicellulose was the second component to start decom-
3.2 posing, followed by cellulose, in a narrow temperature interval
from about 200 to 400 °C. Based on this discussion, the three local
3.0 minima can correspond to hemicellulose, cellulose and lignin in
2.8
turn.
1.40 1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90 Finally, the activation energy of three major components can be
-1 obtained by Eq. (10): 133.04 kJ/mol for hemicellulose, 175.17 kJ/mol
1000/T (K )
for cellulose and 141.90 kJ/mol for lignin, which is listed in Table 3
Fig. 2. FWO plots for different conversion rates. compared with the values in the literature. Assuming that there is
374 Y. Ding et al. / Energy Conversion and Management 120 (2016) 370–377

0.6

(a) |DDTG|
0.5
d2(m/m0)/dT2×10-3 (K-2)

0.4 60 K/min

0.3
LM II

0.2
LM I

0.1
LM III

0.0
400 500 600 700 800 900
T (K)
12

(b) |DTG|
10
Peak II

Fig. 6. Absorbance spectra stack plot of TG-FTIR at 20 K/min.

d(m/m0)/dT×10-3 (K-1)

6 against temperature. Fig. 6 indicates that most of the gases are

Peak I
evolved between 500 K and 700 K, which basically agree well with
4 the DTG curves.
Based on the K-K method, the corresponding peak temperature
2
is 587 K, 645 K and 690 K for hemicellulose, cellulose and lignin at
Peak III 20 K/min, respectively, while 610 K, 666 K and 719 K at 60 K/min.
The FTIR spectra curves in accordance with these peak tempera-
0
tures are shown in Figs. 7 and 8.
400 500 600 700 800 900
T (K)
The variations of spectrum are related with infrared (IR) absorp-
tion, which is restricted to compounds with small energy differ-
Fig. 5. Estimation of peak locations at 60 K/min: (a) |DDTG| and (b) |DTG|. ences in the possible vibrational and rotational states. For a
molecule to absorb infrared, the vibrations or rotations within a
molecule must cause a net change in the dipole moment of the
Table 3
molecule. Therein, molecule vibrations are more important for FTIR
Activation energy of cellulose, hemicellulose and lignin by the K-K method.
analysis, which is mainly composed of stretching and bending [39].
Component Activation energy (kJ/mol) During the analysis, the spectrum can be divided into two parts:
K-K Ding et al. Branca et al. Zhang et al. functional groups region (4000–1333 cm1) which is used to iden-
method [4] [37] [38] tify the presence and absence of functional groups, and complex
Hemicellulose 133.04 131.19 147.00 179.84 fingerprint region (1333–667 cm1) in which the absorption is less
Cellulose 175.17 151.73 193.00 240.23
Lignin 141.90 130.78 181.00 165.61
0.06

0.04 20 K/min
no interaction among the three major components [35], the total Peak I (Hemicellulose)
activation energy of beech wood should be in the range of 133.04 0.02
to 175.17 kJ/mol, which just covers the activation energy computed
by the FWO and KAS methods (148.63–174.44 kJ/mol for FWO and 0.00
146.84–172.21 kJ/mol for KAS). So the results based on the K-K 0.06

method are reasonable from this point of view. Peak II (Cellulose)

Absorbance

0.04
Furthermore, based on the peak locations of different compo-
nents in Fig. 5, the decomposing temperature range of hemicellu- 0.02
lose and cellulose can be roughly estimated as being between
500–650 K and 550–700 K, and lignin appears to decompose 0.00
0.02
throughout the whole pyrolysis process.

0.01
Peak III (Lignin)
4.3. Fourier transform infrared analysis of gas products

0.00
A typical 3D spectrogram from the TG-FTIR is shown in Fig. 6,
which provides related information both as a function of 4000 3500 3000 2500 2000 1500 1000 500
wavenumber and temperature. The composition of produced gases Wavenumber (cm-1)
can be determined by the characteristic wavenumber bands, while
the yield history of the products can be obtained by the absorbance Fig. 7. Absorption spectra of different peaks at 20 K/min.
 Y. Ding et al. / Energy Conversion and Management 120 (2016) 370–377
0.12
0.10
0.08 60 K/min Peak I (Hemicellulose)
0.06
0.04
0.02
0.00
0.12
0.10
Peak II (Cellulose)
0.08
Absorbance
0.06
0.04
0.02
0.00
0.06
0.04
Peak III (Lignin)
0.02
0.00
4000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1)
Fig. 8. Absorption spectra of different peaks at 60 K/min.
conspicuous [40]. Therefore, the evolved gases can be identified by
the variations of spectrum. The different spectra observed in peak
I-III, may be caused by the difference of inherent structures and
compositions among hemicellulose, cellulose and lignin [41]. The
molecule of hemicellulose, cellulose and lignin can be expressed
as [C5(H2O)4]n, [C6(H2O)5]n and [C10H12O3]n, respectively. Hemicel-
lulose has a random, amorphous structure with little strength,
which is easily hydrolyzed by a dilute acid or base. However, cellu-
lose is crystalline, strong and resistant to hydrolysis with a very
long polymer of glucose units. Lignin is heavily cross-linked, filling
the three dimensions of biomass [41].
In general, the spectra of three peaks pyrolysis are consistent
with that of common wood samples: strong broad OH stretching
(4000–3300 cm1), C-H stretching in methyl and methylene
groups (3000–2800 cm1), a strong broad superposition with sharp
and discrete absorptions (1750–1000 cm1) [42], and a conspicu-
ous spectrum band of CO2 corresponding to 2400–2260 cm1 [9].
Comparing the absorbance among the three peaks, H2O (4000–
3500, 1800–1300 cm1) is generated from the decomposition of
various oxygen-containing groups [33] and the cracking of alipha-
tic hydroxyl groups in the lateral chains [43], while the amount of
H2O produced from lignin (peak III) is much less than from hemi-
cellulose and cellulose, which is consistent with the experimental
results of Wang et al. [44] when they analyzed the FTIR spectra
of separate hemicellulose, cellulose and lignin. The generation of
CO2 (2400–2260, 680–660 cm1) is attributed to the cracking and
reforming of functional groups of carboxyl (C@O) and COOH [45],
cracking and abscission of CAC and CAO bonds connected with
the main branch of hemicellulose, cracking of C@O groups in cellu-
lose, and breaking of lateral CAC bonds [43]. The spectra within
2260–2000 cm1, including characteristic peak values of 2110
and 2180 cm1, indicate the formation of CO. The releasing of CO
is mainly from the cracking of carbonyl (CAOAC) and carboxyl
(C@O) [45], and more CO is generated at peak II compared with
the other two peaks.
In addition to these small molecular weight gases (H2O, CO2 and
CO) during the pyrolysis process, a strong absorption band within
3100–2750 cm1 shows the existence of hydrocarbons, especially
methane [43]. The release of methane can be attributed to the
cracking of methoxyl-O-CH3, which coexists in hemicellulose,
cellulose and lignin [45]. It is noted that there is a more obvious
peak at 3016 cm1 corresponding to lignin pyrolysis, which is also
375
found in the FTIR spectra during the separate lignin pyrolysis pro-
cesses [44]. This may be caused by the abundant O-CH3 content in
lignin. Moreover, the most significant band during pyrolysis is
within 1900–1600 cm1, which indicates the presence of organic
compounds with carbonyl group (C@O), which is related to numer-
ous organic species, such as aldehydes, esters and ketones [33].
Formaldehyde may be produced by the fragmentation of the
hydroxymethylene group (ACH2OH) in the phenyl propane lateral
chains [43]. Meanwhile, the band at 1400–1300 cm1 indicates the
existence of OAH, corresponding to the presence of alcohols and
phenols [43], especially methanol according to the characteristic
bands at 3100–2750 cm1 and 1200–1000 cm1. The gas products
and functional groups mentioned above are also summarized in
Table 4.
In addition to C, H, O described above, there is also 0.16% N in
the element analysis of beech wood. However, the absorbance of
N-products is not enough to be distinguished due to the little pro-
portion of N. For example, the spectra of HCN (3400–3200 cm1,
500 1700–1500 cm1 and 1000–900 cm1) and NH3 (3400–3200 cm1
and 800–600 cm1) are not conspicuous [40]. So N-products are
not involved in our analysis of main gas components.
Furthermore, comparing the absorption spectra in Figs. 7 and 8,
the spectra are basically the same at the three peaks for 20 K/min
and 60 K/min, implying that the heating rate has little influence on
the evolved gas species.
Considering the same methodology and exact operation for the
FTIR measurement, the concentration variation of gas species can
be reflected by the change of IR peak heights [33]. Especially,
according to the widely applied Lambert–Beer Law [43], the absor-
bance value at a specific wavenumber is linearly correlated with
the gas concentration. Therefore, the distribution of gas composi-
tion against temperature can be obtained after the evolved gas
species are identified. The specific peak wavenumbers of small
molecular weight main gas species during the beech wood pyroly-
sis process are identified as: CO2, CO, methane, methanol and
formaldehyde. It is worth noting that some diatomic molecule
gases (such as H2, O2, N2) cannot be detected using FTIR because
of the absence of a dipole [40].
The profiles of detected gases with temperature increase during
the beech wood pyrolysis at 20 K/min and 60 K/min are plotted in
Fig. 9a and b, respectively. The distributions of different gas com-
ponents are basically the same as the DTG curves corresponding
to different heating rates, especially for the formaldehyde, metha-
nol and CO2. Obvious shoulders and peaks still appear in the
evolution of gases. The amount produced of these five components
in the order of most to least formed is formaldehyde > CO2 or
methanol > methane > CO. In particular, at peak II, the amount of
formaldehyde is almost triple the amount of methanol and ten
times the amount of methane.
Comparing the evolution between 20 and 60 K/min in Fig. 9, the
whole variant tendency is almost identical except for CO2. When
the temperature reaches peak III, CO2 begins to decline at
20 K/min, while a slight increase appears at 60 K/min. The reason
for the slight increase may be attributed to the coking polymeriza-
tion reaction [9]. As the temperature increases to peak III, about
Table 4
Gas products and functional groups by FTIR in the present study.
Gas products/functional groups Wavenumber range (cm1)
H2O 4000–3500, 1800–1300
ACH3, ACH2A 3100–2750
CO2 2400–2260, 680–660
CO 2260–2000
Carbonyl group (C@O) 1900–1600
Hydroxyl group (AOH) 1400–1300
376 Y. Ding et al. / Energy Conversion and Management 120 (2016) 370–377

0.06 tions by the K-K method. CO, CO2, methane, methanol and
formaldehyde were identified by FTIR spectra, and their evolutions
Peak II
(a) 20 K/min were still similar at different heating rates. The amount of these
0.05 CO2
five components produced was formaldehyde > CO2 or metha-
CO
nol > methane > CO. Furthermore, the derived kinetic parameters
Methane
0.04 and profiles of evolved gases can be embedded into pyrolysis
Methanol
Absorbance

Formaldehyde model and coupled with multi-component combustion model in

0.03 the further simulation process.
Peak I

0.02 Acknowledgement

The authors would like to acknowledge financial support spon-

0.01 Peak III
sored by National Basic Research Program of China (973 Program,
Grant No. 2012CB719704) and Fundamental Research Funds for
0.00 the Central Universities (WK2320000034).
400 500 600 700 800 900
Temperature (K)
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