Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

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Journal of Analytical and Applied Pyrolysis

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

The effect of the biomass components lignin, cellulose and hemicellulose on TGA
and xed bed pyrolysis
Luisa Burhenne a, , Jonas Messmer a , Thomas Aicher a , Marie-Pierre Laborie b
a
b

Fraunhofer-Institute for Solar Energy Systems ISE, Heidenhofstr. 2, 79110 Freiburg, Germany
Institute of Forest Utilization and Work Science, University of Freiburg, Werthmannstr. 6, 79085 Freiburg, Germany

a r t i c l e

i n f o

Article history:
Received 19 October 2012
Accepted 13 January 2013
Available online 31 January 2013
Keywords:
Biomass
Pyrolysis
TGA
Fixed bed

a b s t r a c t
Thermochemical conversion of biomass has been studied extensively over the last decades. For the design,
optimization and modeling of thermochemical conversion processes, such as xed bed pyrolysis, a sound
understanding of pyrolysis is essential. However, the decomposition mechanism of most biomass types
into gaseous, liquid, and solid fractions is still unknown because of the complexity of pyrolysis and
differences in biomass composition.
The aim of this study was to nd characteristic differences in the pyrolysis behavior of three widely used
biomass feedstocks to optimize the performance of industrial xed bed pyrolysis. This aim was achieved
in three steps. First, devolatilization kinetics during pyrolysis of three biomass types was investigated
in a thermogravimetric analyzer (TGA). Then, a one-step multi-component pyrolysis model with three
independent parallel reactions for hemicellulose, cellulose and lignin was derived to correlate the kinetics
with single component decomposition and to identify their amount in the biomass sample. In a nal
step, the ndings were tested in a xed bed reactor at laboratory scale to prove applicability in industrial
processes.
Three types of biomass were chosen for this investigation: wheat straw, rape straw and spruce wood
with bark. They represent biomass with a high cellulose, hemicellulose and lignin content, respectively.
Since lignin is the most stable and complex of these three biomass components, its amount is assumed
to be the main controlling factor in the thermochemical decomposition process.
The thermogravimetric (TG) curve of spruce wood with bark was found to shift to about 20 K higher
temperatures compared to the TG curves of straw and rape straw. This result indicates that a higher activation energy is needed to decompose woody biomass, which contains a higher amount and a different
type of lignin than straw. Three wood decomposition phases were distinguished from the negative rst
derivatives curves (DTG): a shoulder during hemicellulose decomposition, a peak during cellulose decomposition and a smaller rise during lignin decomposition. By comparison both herbaceous biomass types
decomposed in only two phases at lower temperatures. The decomposition of the herbaceous, and woody
biomass samples was completed at about 830 K and 900 K, respectively, leaving only a solid residue of
ash. The derived pyrolysis model estimated the composition and described the devolatilization curves
of each biomass with sufcient accuracy for industrial processes, although the same activation energy
set, taken from the literature, was used for each biomass. In the xed bed pyrolysis experiments similar
characteristics were found to those in the TGA experiments. Herbaceous biomass with a higher cellulose
and hemicellulose content decomposed faster and produced a larger fraction of gaseous products than
woody biomass with a higher lignin content. According to the assessment of the product distribution,
performed after each experiment, woody biomass pyrolysis led to a larger fraction of solid products
than herbaceous biomass pyrolysis. We conclude that industrial xed bed pyrolysis can be optimized for
different biomass feedstocks with a specic composition of cellulose, hemicellulose and lignin.
2013 Elsevier B.V. All rights reserved.

1. Introduction

Corresponding author.
E-mail address: luisa.burhenne@ise.fraunhofer.de (L. Burhenne).
0165-2370/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.01.012

Plant biomass, a composite material mainly comprised of hemicellulose, cellulose, lignin, is an ideal renewable resource for the
generation of heat and power via thermochemical processes such
as xed bed gasication. However, with the growing biomass needs
for both bioenergy and biomaterials, the availability of biomass

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L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

feedstock for the thermochemical conversion processes is becoming more and more limited, especially in highly populated regions.
Therefore, technical processes need to be improved so that a wide
range of biomass types, including biomass waste and side products, can be converted into synthesis gas that can be used directly
for heat and power production. In order to optimize any conversion process and to ne-tune process parameters to the specic
feedstock characteristics, a detailed knowledge about the way in
which the biomass composition inuences the conversion behavior
is important.
Pyrolytic decomposition, the core reaction in all thermochemical conversion processes, is crucial to the biomass decomposition
into gaseous, liquid, and solid fractions [1]. In xed bed gasication, pyrolysis is caused by the heat of hot gases released during
partial combustion. The pyrolysis temperature and heating rate
are given by heat transfer from the gas to the biomass particle
on the one hand and by heat transfer within the particle itself
on the other hand. Since heat conductivity in biomass particles is
known to be very low, biomass pyrolysis during xed bed gasication can be compared to conventional slow pyrolysis. Hence,
pyrolysis temperatures, decomposition rates, product composition
and yields are inuenced by both heat transfer and chemical reactions. Both vary with the biomass composition since the three
polymeric constituents, namely lignin, cellulose and hemicellulose, have different internal energy as well as heating values [2].
As a result they differ markedly in their thermal stability with
lignin being the most stable of all structural components. According to Yang et al. [3], lignin decomposes constantly in a wide
range of temperatures compared to cellulose and hemicellulose,
which decompose in a small temperature interval between 573 K
and 673 K due to their homogeneous structure. According to Yang
et al. [3], lignin does not decompose completely until temperatures up to 973 K are reached. It was also found that pyrolysis of
woody biomass with high lignin content is an overall endothermic reaction, whereas pyrolysis of herbaceous biomass, with lower
lignin content, involves an exothermic reaction [3]. Furthermore,
the amount of lignin is assumed to be the main controlling factor for the pyrolytic decomposition rate, the product yields and
composition.
So far, numerous studies on the pyrolytic decomposition of the
main components have been carried out [4]. Most have focused
on the pyrolysis of several milligrams of the pure biomass components lignin, cellulose and xylan or wood from specic tree species
[5]. However, the decomposition behavior of different types of real
biomass, such as herbaceous and woody biomass, has rarely been
investigated with the aim of correlating it to the decomposition
characteristics of its main constituents. Such an approach could be
used to optimize industrial processes.
In order to predict the decomposition behavior of any biomass,
rst the characteristics of the single components need to be identied [6]. Some authors have attempted to predict thermal and
kinetic behavior of biomass from its composition simply by the
superposition of the decomposition of the single components.
Couhert et al. [7] have shown that the correlation between biomass
gas yields and the cellulose, hemicellulose and lignin fractions is
not very accurate. Nevertheless, since the components differ signicantly in their decomposition behavior [8], it is possible to
determine clear trends in decomposition time, reaction enthalpy,
gas yield and composition of any biomass according to its composition of lignin, cellulose and hemicellulose [1]. Grnli et al. [6]
developed a one-step multi-component pyrolysis model consisting
of three parallel, independent reactions with three activation energies: each one for cellulose, hemicellulose and lignin. Using this
model approach, high temperature (>553 K) degradation of nine
woody biomass types was described with accuracy. To the best
of our knowledge, this multi-component pyrolysis model has not

been used to compare pyrolysis of woody biomass to non-woody

biomass or to identify the amount of cellulose, hemicellulose and
lignin in a biomass sample.
To compare the results of the TGA experiments with biomass
pyrolysis in technical processes, some authors used installations
such as packed bed pyrolysis reactors [3,8]. However, still in these
experiments, only very small pure wood component samples were
analyzed. There is still a gap between basic research on pyrolysis
on a micro-scale and the research on applied pyrolysis processes.
Almost no published studies could be found in which results of TGA
with different biomass types were compared to packed bed reactors
using large sample masses (>100 g).
The objectives of this work were to identify general trends in the
decomposition behavior of lignocellulosic biomass from biomass
sources differing in cellulose, hemicellulose and lignin fractions,
and then to express these trends in a simple pyrolysis model to
test their relevance for the performance optimization of xed bed
pyrolysis.
Based on the literature reviewed above, we hypothesized that
the lignin content of any biomass feedstock is the main controlling factor in pyrolysis in industrial processes. In particular we
proposed that a high lignin content leads to a slow decomposition and low product gas yield and that devolatilization is initiated
at higher temperatures. We tested this hypothesis by pyrolysing
three widely used feedstock types, each with a characteristic high
cellulose, hemicellulose and lignin contents in a TGA. In the TGA
heat or gas transfer is not a limiting factor and therefore thermogravimetric behavior purely reects the pyrolysis reactions. Wheat
straw, rape straw and spruce wood with bark was used to represent biomass feedstocks with a high cellulose, hemicellulose and
lignin content, respectively [1,9,10]. Then, we derived a theoretical
one-step devolatilization model to identify the biomass composition and to relate it with the observations. To prove applicability of
the ndings on industrial processes, the same biomass feedstocks
were pyrolysed in a xed bed reactor that was purged with hot
nitrogen as carrier gas.

2. Materials and methods

2.1. Feedstocks
Three types of biomass were chosen to represent feedstocks
with different compositions: wheat straw for its high cellulose
content, rape straw for its high hemicellulose content and spruce
wood pellets with bark for its high lignin content. The wheat and
rape straw are agricultural by-products from cultivation near Rot
am See in Germany. The straw samples were provided by S + K
GmbH Haus und Energietechnik. The spruce wood pellets were
made of Norway spruce with bark (Picea abies (L.) Karst.) harvested in the Hochsauerland (forestry administration North-Rhine
Westphalia Germany) and provided by the Pusch Ag in Marienrachdorf, Germany. All samples were provided as cylindrical pellets
with a diameter of 520 mm and a length up to 30 mm. Elemental analysis of the biomass samples was conducted in the chemical
laboratory of University Freiburg using a fully automatized elemental analyzer (VarioEL, Elementaranalysensysteme GmbH). Biomass
composition in terms of C, H and O as well as the ash content is
given in Table 1. The proximate analysis was provided by courtesy
of the TEER Institute of RWTH Aachen following the standard DIN
51719.
Biomass composition in terms of cellulose, hemicellulose and
lignin is derived by atomic balance of the components elemental formula following the method of Ranzi et al. [1]. For cellulose
and hemicellulose the elemental formulas for all biomasses are
assumed to be C6 H10 O5 and C5 H10 O5 , respectively. Lignin is a

L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

179

Table 1
Ultimate and proximate analysis of the biomass samples by wt.%.

Wheat straw
Rape straw
Spruce + bark

Moisture

Volatiles

Fixed carbon

Ash

43.15
44.47
46.43

6.21
6.35
6.21

45.92
45.23
42.19

4.2
3.7
6.9

73.2
76.5
68.9

18.2
16.1
19.3

4.39
3.69
4.88

Table 2
Composition of dry biomass by wt.% calculated by atomic balance compared to Refs. [5,9,12].
Calculated by atomic balance

Literature

Cellulose

Hemicellulose

Lignin

Cellulose

Hemicellulose

Lignin

Ref.

Wheat straw

38

36

22

38.0
33.2
28.8

29.0
24.0
39.1

15.0
15.1
18.6

[5]
[9]
[12]

Rape straw

36

37

24

37.6

31.4

21.3

[9]

Spruce + bark

42

27

26

41.0
50.8

24.3
21.2

30.0
27.5

[5]
[12]

product of polymerization of three types of monolignols, i.e. pcoumaryl, coniferyl, and synapyl alcohols, incorporated into lignin
in the form of p-hydroxyphenyl (H type lignin), guaiacyl (G type
lignin), and syringyl (S type lignin), respectively [11]. The elemental formulas of H, G and S type lignin are C9 H10 O2 , C10 H12 O3 and
C11 H14 O4 , respectively. Softwoods such as spruce contains mainly
G type lignin, whereas straw contains about 45% of H, 46% of G and
9% of S type lignin [11]. Hence, the representing elemental formula
of lignin in spruce with bark is C10 H12 O3 . The elemental formula of
lignin and in both straws is C10.4 H12.7 O3.4 , given by their proportions of each lignin type. The calculated cellulose, hemicellulose
and lignin mass fractions are in line with values provided in the
literature [5,9,12] (Table 2). The component fractions calculated by
atomic balance are very sensitive to changes of the input parameters, meaning that the biomass composition can change to a great
extent with only a minor change in H, C or O ratio. Therefore, the
biomass composition was additionally estimated by curve tting
experimental data to a theoretical three-component devolatilization model based on input parameters from the literature.
Before conducting the experiments, the samples were ovendried for 24 h at 105 C. For the TGA experiments, the dry biomass
pellets were ground to a particle size smaller than 0.3 mm. This
particle size has been proven suitable for preventing heat and mass
transfer effects during the experiments [13].
2.2. Devolatilization kinetics in TGA
Thermogravimetric experiments were carried out in a differential thermogravimetric analyzer (PerkinElmer Pyris 1 TGA)
provided courtesy of FoBaWi Institute, Albert-Ludwigs University,
Freiburg. The precision of the temperature measurement was 2 K.
For each sample, 5 mg of dried and ground biomass was heated
from 50 C up to 700 C under dynamic conditions at a heating rate
of 20 K/min. The TGA experiments were carried out at atmospheric
pressure and the equipment was purged with a nitrogen ow of
20 mlN min1 . Each experiment was repeated at least three times.

each corresponding to the decomposition of one of the components

cellulose, hemicellulose or lignin [13]. Pure additive behavior of the
components and rst order kinetics are assumed for modeling the
decomposition reaction of each component.
The overall conversion is expressed by the calculated normalized sample mass Xcalc = (m mash )/(m0 mash ) 100 %, where m0
is the initial sample mass, m the actual sample mass and mash the
mass of the ash in each sample, given in Table 1. The actual sample
3
mass m at any time can be described by m(t) =
x m(t) + mash ,
i=1 i
where xi is the mass fraction of cellulose, hemicellulose and lignin,
respectively. Hence, the total normalized sample mass Xcalc can
3
3
x m/(m0 mash ) 100% =
X . Xcalc
be written as Xcalc =
i=1 i
i=1 i
varies from 0% to 100% and is calculated from the sum of the individual normalized sample mass loss rates dXi /dt, each corresponding
to the decomposition of component i = hemicellulose, cellulose and
lignin.

3

 dX
xm
dX calc
d
i
i=1 i
=
=
100%
dt
dt
dt m0 mash
3

(1)

i=1

The conversion of each component Xi is described by a rst order

kinetic reaction as:
dX i
m(t)
= ki (T )Xi = ki (T )xi
100%
m0 mash
dt

(2)

The rate coefcient ki (T) for each component i is described

with the Arrhenius-type temperature-dependent equation
ki (T) = k0,i exp[E(A,i) /RT], where EA,i is the apparent activation
energy. Grnli et al. [6] found activation energies EA,i that are
suitable for a wide range of woody biomass types. Differences
in the decomposition behavior of the biomass types in terms of
reaction temperatures and yields of solid products (char) were
accounted for by the pre-exponential factor k0,i . The values for
hemicellulose, cellulose and lignin found in the literature [6,14]
that were applied in this study for the estimation of the biomass
composition are listed in Table 3.

2.3. Theoretical devolatilization model

Correlation analysis was performed between the different
reaction phases of the biomass and the single component decomposition using the multi-component model proposed by Grnli
et al. [6] in order to estimate the biomass composition in terms
of cellulose, hemicellulose and lignin. According to this model, the
decomposition of biomass is described by three parallel reactions,

Table 3
Parameters for the one-step three-component devolatilization mechanism of cellulose, hemicellulose and lignin from spruce [6].

Cellulose
Hemicellulose
Lignin

EA,i (kJ/mol)

k0,i (1/s)

236
100
46

1017.43
106.4
100.58

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L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

Fig. 1. Process ow chart of the laboratory-scale pyrolysis test unit for investigating xed bed pyrolysis.

A nonlinear least squares algorithm was used to optimize the

calculated correlation curve by identifying the mass fractions xi of
cellulose, hemicellulose and lignin that minimize the function S
in Eq. (3). S is a function of the mean experimental DTG curves
dXi,meas /dt and the calculated dXi,calc /dt values that can be calculated
as follows:
S=

N

((dX i,calc /dt) (dX i,meas /dt))2
i=1

(3)

where N is the number of points on the resulting curve. For a

rst parameter estimation the component fractions calculated by
atomic balance were taken (Table 2). The goodness of the optimized
curve was evaluated with the deviation between the measured and
the calculated curves at the optimal set of parameters (Eq. (4)).

Deviation (%) = S 100%

(4)

pyrolysis products along with the carrier gas left the reactor on the
upper side and were washed in a canister lled with rapeseed oil
(F 1). The gaseous products were cooled down with a thermostat.
A sidestream of the product gas was cleaned and supplied to an
online gas analyzer (GA) in order to analyze the gas composition in
terms of CO, CO2 , H2 and CH4 . Other gases, e.g. O2 , N2 , alkanes, and
alkenes, were analyzed with a gas chromatograph (GC). Pressure
sensors were installed to detect any blocking in the washing and
cooling sections. The volume ow of product gas was determined
through the N2 balance after gas analysis according to Eq. (5).
V i =

xi
V N2
xN2

(5)

where i = CO, CO2 , CH4 , H2 . V N2 denotes the volume ow of nitrogen.

V i and xi denote volume ow and volumetric fraction of component
i, respectively.

2.4. Fixed bed pyrolysis

3. Results and discussion

To investigate pyrolysis in a xed bed, a laboratory-scale test

reactor was designed and built. In this laboratory test reactor, 500 g
of biomass was heated up at a slow heating rate of about 20 K/min
with hot nitrogen passing through the bed until a bed temperature
of 773 K was reached. In Fig. 1 the process ow chart of the pyrolysis
experimental setup is shown. The reactor consisted of a heat resistant pipe (DN 100) constructed from 1.4828 stainless steel with
an inner diameter of 109.4 mm. The biomass entered the reactor
through the lling air lock in the upper part, which contains of a
pinch valve (V1) and a manual gate valve (S1), and then fell into the
reaction chamber. In the reactor, the biomass was held by a movable
grid. The reaction chamber has a volume of 4 l. With the movable
grid, the pyrolysis residues were removed through the char outlet after each experiment. The temperature prole in the reactor
was measured with eight thermocouples (TIR 1 to TIR 8) arranged
horizontally in the center of the reactor chamber. The carrier gas
was heated with a spiral heating element (TIC 1) and an oven. The
nitrogen volume ow rate for STP conditions was set by a mass
ow controller (MFC type 1559A of MKS Instruments Deutschland
GmbH). The hot gas was supplied to the reactor via a lance nozzle
and ew upwards through the packed bed of biomass. The volatile

3.1. Devolatilization kinetics in TGA

For the experiments in the thermogravimetric analyzer (TGA),
the mean normalized sample mass X of all samples for one biomass
type was expressed as function of temperature between 50 K and
700 K. The results are shown in Fig. 2.
The maximum standard deviation between the measured curves
was 1.88%, 1.07% and 1.66% for wheat straw, rape straw and spruce
with bark, respectively. The small change in sample mass below
450 K was attributed to vaporization of moisture, and therefore
omitted from this study. The pyrolytic decomposition of all samples
began slowly at about 480 K with the rate increasing at about 510 K
for the herbaceous biomass samples and at 530 K for the wood samples. The thermogravimetric (TG) curve for wood with bark shifted
to higher temperatures, by about 20 K, compared to the TG curves
for herbaceous biomass types. This result indicates that a higher
activation energy is needed to decompose woody biomass which
can be explained by the higher lignin content of the wood. Lignin
is an aromatic polymer compound with three-dimensional links in
an alkyl-benzene structure. During isolation, its structure is modied [15]. Hence, the exact initial structure of lignin in wood is still

L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

Fig. 2. TG and DTG curves of three biomass types at a heating rate of 20 K/min. Left
hand side y axis: TG curves; right hand side axis: DTG curves.

unclear. Composition, amount and type of lignin (H, G, S type) varies

from tree species to tree species, even in wood from different parts
of the same tree. However, all lignin is known to be very stable and
more difcult to decompose than cellulose or hemicellulose [16].
Lignin decomposes slowly over a large temperature range up to
a pyrolysis temperature of 1173 K [8]. Another possible reason for
this temperature shift is the high amount of tannins which in spruce
bark can reach up to 10 wt.%. Tannins are also phenolic compounds
derived from the same biosynthetic pathways as lignin. The impact
of biomass extractives, e.g. tannin, and ash content on the pyrolytic
decomposition will be investigated in subsequent studies.
The decomposition of the herbaceous and woody biomass samples was completed at about 830 K and 900 K, respectively. The solid
residue of the wheat straw, rape straw and spruce with bark samples was 5%, 4% and 9%, respectively. Comparing these amounts
to the proximate analysis of the biomass samples (Table 1) it can
be seen that the solid residue of the herbaceous biomass samples
was only ash. The amount of solid residue of the woody biomass
samples however, is higher than their ash content. This indicates
an incomplete decomposition of the wood which was explained by
the higher lignin content of the woody samples.
The TG curves of wheat straw and rape straw were very similar,
except that the rape straw decomposition peak occurred at higher
temperatures than that of wheat straw. This is explained by the
differences in hemicellulose structure between both straw samples. Hemicellulose comprises a group of biopolymers which are
branched polysaccharides [17]. They are more complex than the
cellulose structure. Hemicelluloses are thermally the most unstable components of biomass. Therefore, hemicellulose decomposes
faster and at lower temperatures than cellulose and lignin.
In agreement with the literature [14], the rst negative derivative of the TG (DTG) curve of the spruce and bark samples showed
three decomposition phases: decomposition in the rst phase commenced at 500 K and nished with a shoulder at 585 K. The second
phase, between 610 and 680 K, showed a peak at 644 K, indicating the maximal decomposition rate of 0.25 wt.% K1 . The third
phase occurred between 690 and 880 K with a maximal decomposition rate of 0.074 wt.% K1 at a temperature of 830 K. Di Blasi
[14] reviewed a wide range of pyrolysis data and concluded that,
for slow heating rates, hemicellulose decomposes in a temperature
range of 498598 K. Therefore, we attributed this peak to hemicellulose decomposition. The next phase, between 610 and 680 K with
a peak at 644 K, was attributed to cellulose decomposition. According to Di Blasi [14], cellulose decomposes between 598 and 648 K.

181

The third phase, indicated by a slight rise in mass loss rate between
690 and 880 K (Fig. 2), may be attributed to lignin decomposition.
Yet there is no mention of a rise due to lignin decomposition in the
literature [5,6,14]. Alternatively, this rise may be attributed to secondary reactions of carbon-containing residues. Fisher et al. [18]
have shown that, at temperatures above 673 K, a weight loss due
to thermolysis of carbon containing residues does takes place. To
understand the true nature of this decomposition rise at temperatures between 690 K and 880 K, further investigation is needed.
Both herbaceous biomass feedstocks decomposed in only two
phases. The rst regime was found between 500 and 670 K with
a maximal decomposition rate of 0.275 wt.% K1 at 600 K, and
0.26 wt.% K1 at 620 K for wheat straw, and rape straw, respectively.
This regime was attributed to the decomposition of hemicellulose and cellulose, which can overlap at these temperatures [14].
The second regime occurred with a much smoother and smaller
rise at 760 K and 790 K for wheat straw and rape straw, respectively. The nature of this rise needs to be investigated further in
subsequent studies, for the same reasons as stated above. Yang
et al. [8] investigated the pyrolysis characteristics of pure hemicellulose, cellulose and lignin in a pack bed loaded with 2 g of
the sample and a particle size of 0.050.1 mm. At a heating rate
of 10 K/min they found maximum mass loss rates of 7 wt.% K1 ,
1 wt.% K1 and 0.3 wt.% K1 for cellulose, hemicellulose and lignin,
respectively. In the TGA experiments carried out in this study,
the maximum mass loss rates attributed to cellulose decomposition were 0.275 wt.% K1 , 0.26 wt.% K1 and 0.25 wt.% K1 , the
maximum mass loss rates attributed to hemicellulose decomposition were 0.15 wt.% K1 , 0.13 wt.% K1 and 0.11 wt.% K1 and
the maximum mass loss rates attributed to lignin decomposition
were 0.035 wt.% K1 , 0.02 wt.% K1 and 0.074 wt.% K1 for wheat
straw, rape straw and spruce + bark, respectively. The mass loss
rates, much smaller than those reported in the literature, may be
caused by the fact that Yang et al. [8] used pure biomass components, whereas, in this study, real biomass is used. Couhert et al
[7] stated that decomposition of pure components differs from
real biomass because the pyrolysis reactions are less hindered
by interactions with other components. However, in accordance
with the results reported in the literature [8], cellulose decomposition resulted in a much higher decomposition peak compared
to lignin decomposition. The maximum mass loss rates of cellulose and hemicellulose were similar for all biomass types, whereas
the peaks of lignin showed greater variations between the biomass
groups. This is explained by the different compositions of lignin,
which depends strongly on the biomass type [16]. After pyrolysis of
the wood + bark samples, 3.5% carbon-containing material was left
at 973 K, whereas herbaceous biomass samples were decomposed
completely at about 830 K. In pyrolysis experiments with wood,
Rath et al. [19] found a linear correlation between the reaction
enthalpy of pyrolysis and the nal yield of solid products. Char formation was found to be an overall exothermic reaction, competing
with the endothermic volatile formation processes during pyrolysis. Studying the pyrolysis enthalpy of cellulose, Mok and Antal [20]
also found a linear correlation between reaction enthalpy and nal
char yield. These studies [20] seem to conrm the results obtained
here, and support the hypothesis that higher lignin content leads
to a higher char yield and, hence, a higher reaction enthalpy.
3.2. Theoretical devolatilization model
The theoretical decomposition behavior was described with
a rst order multi-component devolatilization model taking into
account three independent one-step devolatilization mechanisms
for hemicellulose, cellulose and lignin. Kinetic parameters, namely
the pre-exponential factors k0,j and the activation energies EA,i ,
were taken from the literature [6,14]. The mass fractions xi

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L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

Fig. 3. Optimization of calculated decomposition curves compared to measured TGA and DTG curves at a heating rate of 20 K/min: (a) wheat straw, (b) rape straw and
(c) spruce + bark. Measured values are represented by solid lines and simulated values (dashed lines) are superpositions of simulated decomposition curves of cellulose,
hemicellulose and lignin, respectively (dotted curves).

of cellulose, hemicellulose and lignin were obtained by tting

the experimental DTG curves of each biomass sample to the
devolatilization model. The calculated curves were optimized for
all biomass samples by the minimizing the function S in Eq. (3). As
starting values, the component mass fractions calculated by atomic
balance were taken (Table 2).
In accordance to the literature [1,9,10], wheat straw showed
the highest cellulose content, rape straw the highest hemicellulose content and spruce wood with bark the highest lignin content
with deviations between the measured and the calculated curves
smaller than 4.3%, 5.8% and 4.6%, respectively (Table 4). The estimated cellulose mass fractions of all biomass samples were below
the reported values in the literature [5,9,12]. Cellulose decomposition is the fastest of the three decomposition reactions and may
therefore be transport limited under the conditions of the TGA
experiments, resulting in a decrease of the mass loss rate. Since
the only adjustable parameters of the decomposition model are

Table 4
Composition of dry biomass, estimated by optimization of decomposition model in
wt.%.

Wheat straw
Rape straw
Spruce + bark

Cellulose

Hemicellulose

Lignin

Maximal
deviation

28.5
21.2
27.0

26.7
37.3
24.2

40.4
37.8
43.9

4.3
5.8
4.6

the mass fractions, an underestimation of the mass loss rate leads

to an underestimation of the cellulose mass fraction.
Lignin fractions were estimated signicantly higher than
reported in the literature. This is mainly because the decomposition model takes into account only the main biomass components,
ignoring extractives. All other compounds which have comparable
decomposition characteristics to lignin, e.g. tannins, are accounted
for lignin in this model. The estimated hemicellulose factions of all
samples were in line with data from the literature (Table 4).
The estimated hemicellulose factions of all samples were in line
with data from the literature (Table 4).
The optimized correlation curves of all biomass samples are
shown in Fig. 3 as superpositions of the simulated decomposition
curves of cellulose, hemicellulose and lignin. For both herbaceous
biomass samples, the calculated hemicellulose peak appeared at
lower temperatures than in the measured DTG curves (Fig. 3). This
is mainly because the used model parameters from the literature
were given for woody biomass. The lower decomposition temperature indicates that the hemicellulose from herbaceous biomass
has a different structure and lower activation energy than hemicelluloses from woody biomass. With deviations smaller than 4.3%,
5.8% and 4.6%, the optimized correlation curves were in good agreement with the experimental values for the woody and non woody
biomass samples (Fig. 3). Hence, it can be assumed that the model
parameters reported by Di Blasi [14] and Grnli et al. [6] can
be applied for a wide range of woody and non-woody biomass.
These parameters are also within the range of reported values for
other lignocellulosic materials [13,14,21]. To improve the test of

L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

Fig. 4. Volumetric product gas ow in lN/min from 500 g biomass at 773 K under
nitrogen atmosphere in a laboratory counter-current xed bed reactor for pellets of
biomass samples wheat straw (*), rape straw () and spruce with bark ().

this multi-step mechanism and to identify model parameters suitable for herbaceous biomass, the biomass composition in terms
of cellulose, hemicellulose and lignin should be analyzed in further studies. Nevertheless, for engineering purposes, the model
estimates biomass composition and describes decomposition of all
samples with sufcient accuracy for industrial xed bed processes.
Hence, this study conrmed that by describing pyrolysis with a onestep parallel reaction model, the single component characteristics
determine the biomass decomposition. In the model, lignin decomposition is the slowest reaction and hence, the main controlling
factor of the overall pyrolysis process.
3.3. Fixed bed pyrolysis
All three biomass samples were pyrolysed in the laboratory xed
bed reactor. Each experiment was repeated at least three times.
The total product gas ow was calculated by summing all measured product gas ows determined according to Eq. (5). The mean
product gas ow together with the mean bed temperature of each
biomass was plotted over time (Fig. 4). The standard deviation of the
gas release curves was between 9% and 12% and therefore, much
higher than in the TGA experiments. The temperature measurement was delayed by about 2 min due to pyrolysis char covering
the thermocouples.
The decomposition of all biomass samples in the xed bed
began in the temperature range between 420 and 450 K, reaching maximum pyrolysis temperatures between 753 and 793 K.
The initial temperature at which devolatilization commenced differed between spruce samples and the herbaceous wheat and rape
straw samples. Both herbaceous biomass feedstocks showed a similar devolatilization behavior: a rapid increase in the outgassing
volume to a more or less constant volume ow reaching a maximum of 6 lN /min and 5.2 lN /min at about 580 K for wheat straw
and rape straw, respectively. The outgassing of spruce with bark
increased continuously until a maximum of 3.5 lN /min at 680 K was
reached. After reaching the maximum, the outgassing of the herbaceous samples was completed after about 14 min, whereas the
outgassing of the spruce and bark samples decreased more slowly
and was completed after about 18 min. A maximum bed temperature between 770 and 790 K was reached for all samples. Similar to
the TGA experiments, the herbaceous biomass samples revealed a
decomposition peak that was higher, narrower and at lower temperatures (580 K) than the peak of the woody biomass samples (at
680 K). In the xed bed as well and in the TGA experiments, this
behavior was ascribed to hemicellulose decomposition, occurring
typically in the temperature range between 498 and 598 K, followed

183

Fig. 5. Pyrolysis product composition by wt.%, ash-free, in pyrolysis experiments of

500 g pellets of three different biomass types, pyrolysed at 773 K.

by a high cellulose devolatilization between 598 and 648 K [14].

Hemicellulose and cellulose decompose very rapidly compared to
the lignin polymers.
These results indicate that industrial xed bed processes can
be optimized by increasing the process temperature and residence
time with increasing lignin content of the feedstock.
The product distribution of the herbaceous and woody biomass
samples was investigated for all experiments. The samples showed
a liquid fraction of between 48% and 41% for rape straw and wood,
respectively (Fig. 5). The high liquid yield is explained by the low
temperatures in the xed bed. It also indicates short residence
times of the released gases. The gas phase around the solid particles
in the reactor is ushed by the carrier gas and time for relatively
slow secondary reactions such as tar cracking or homogeneous gas
reactions was too short. Previous studies conrm this behavior [22].
The amount of solid products was calculated by subtracting the
ash proportion in the biomass feedstock. The percentage of char in
the biomass samples with lower lignin contents (wheat and rape
straw) was lower than in the samples with a higher lignin content
(spruce + bark). The amount of product gas was calculated using
the N2 balance after gas analysis. With a gas fraction of 20%, herbaceous biomass produced more product gas than woody biomass,
which only produced a gas fraction of 16%. The higher gas yield of
the herbaceous biomass samples is explained by the lower lignin
content in herbaceous biomass (1520 wt.%) compared to wood
(2530 wt.%). According to the literature [3], hemicellulose and cellulose release more gaseous products than lignin. The high mineral
content in the straw biomass might also inuence the total product
gas volume. According to the literature [7], minerals lower the activation energy of pyrolysis reactions, which accelerates exothermic
thermochemical conversion reactions. The effect of the biomass
ash content on the pyrolytic decomposition will be investigated
in further studies. The reason for the larger fraction of solid products produced during pyrolysis of the biomass samples with higher
lignin content (spruce + bark) is that, up to 780 K, cellulose decomposes almost completely and the hemicellulose decomposes to
about 20 wt.%, whereas lignin polymers decompose only to about
of 60 wt.% [5].
According to the analysis of all permanent product gases (Fig. 6),
the CO2 volume in the product gas of the two straw types was
nearly twice that of the CO volume. The difference in the ratio of
CO2 to CO for spruce with bark was lower. The CH4 volume did
not differ signicantly between the samples. Both straw samples
showed a higher H2 fraction compared to the wood samples. In
addition to the direct release of gases during the pyrolysis process,

184

L. Burhenne et al. / Journal of Analytical and Applied Pyrolysis 101 (2013) 177184

gasication can be optimized by adjusting residence times and

temperatures in the reactor according to specic composition in
cellulose, hemicellulose and lignin of the biomass feedstock. In particular, it is recommended that woody biomass containing a higher
lignin content is pyrolysed at higher temperatures and longer residence times than herbaceous biomass with a lower lignin content.
Acknowledgements

Fig. 6. Product gas volumes (CO, CO2 , CH4 , and H2 ) in liters at standard conditions
for pyrolysis experiments of 500 g pellets of three different biomass types, pyrolysed
at 773 K.

The authors acknowledge gratefully the very valuable support

of Dr. Lisbeth Rochlitz, Christian Lintner and the help of all students.
The Institute of Forest Utilization and Work Science (FoBaWi) at the
Albert-Ludwig University in Freiburg, is acknowledged for placing
the TGA equipment at our disposal.
References

heterogeneous and homogeneous gas reactions can take place. The

high amount of CO2 and CO is produced most probably by carbon
oxidation and reduction reactions, e.g. the Boudouard equilibrium.
However, with increasing temperatures, no increase in CO content
could be observed. This is attributed to very low residence times
of the gas in the reaction chamber. At around 773 K, the calculated
gas exchange rate of nitrogen in the reaction chamber is approximately 6 times per minute with a velocity of 4.6 cm/s. To conrm
and quantify this correlation and to investigate the inuence of
other secondary reactions, further studies are needed.
4. Conclusion and outlook
The objectives of this work were to identify characteristic differences in the pyrolysis behavior of three widely used biomass
feedstocks from biomass sources differing in cellulose, hemicellulose and lignin fractions, and then describe these trends in a simple
pyrolysis model to test their relevance for the performance optimization of xed bed gasication. It was shown that the lignin
content of any biomass feedstock is the main controlling factor in
pyrolysis in industrial processes. A higher lignin content leads to
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temperature where devolatilization kicks in.
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(TGA). Wheat straw, rape straw and spruce wood with bark was
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curve of spruce wood with bark was shifted to higher temperatures
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mass fraction of each component and to relate the observations
with the biomass composition. The pyrolysis model could describe
the devolatilization curves of each biomass with sufcient accuracy
for industrial processes, although the same activation energy set,
was used for each biomass. To prove applicability of the ndings
to industrial processes, the same biomass feedstocks were pyrolysed in a xed bed reactor that was purged with hot nitrogen as
carrier gas. In the xed bed pyrolysis experiments, characteristics
were found similar to those in the TGA experiments. Herbaceous
biomass with a higher cellulose and hemicellulose content decomposed faster and produced a larger fraction of gaseous products
than woody biomass with a higher lignin content. Woody biomass
pyrolysis led to a larger fraction of solid products than herbaceous biomass pyrolysis. We conclude that industrial xed bed

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