Article

May 2011 Vol.56 No.14: 14421448

SPECIAL TOPIC: Bioenergy

Energy Science & Technology

doi: 10.1007/s11434-010-4143-y

SPECIAL TOPICS:

Pretreatment of biomass by torrefaction

WANG GuiJun, LUO YongHao*, DENG Jian, KUANG JiangHong & ZHANG YunLiang
School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Received October 29, 2010; accepted January 9, 2011

Agricultural biomass has some drawbacks such as high moisture content, low energy density and wide distribution and as a result,
the cost of transport and storage are high. Moreover, raw biomass has poor grindability so its use in a pulverized boiler or entrained flow gasifier is difficult. Torrefaction is a mild pyrolysis process carried out at temperatures ranging from 200C to 300C
to deal with these problems. The cotton stalk and wheat straw were torrefied in a fix-bed reactor at moderate temperatures (200C,
230C, 250C, 270C and 300C) under N2 for 30 min. The biomass chars after torrefaction had higher energy density and improved grindability characteristics compared with raw biomass and they also showed hydrophobic characteristics. The volatiles
consist of a condensable fraction and a non-condensable fraction. The former mainly contained water and tar (organic products
but mainly acetic acid). The non-condensable products are typically comprised of CO2, CO and a small amount of CH4 and even
trace H2. The volatiles increased with an increase in the torrefaction temperature but the solid yield and the energy yield decreased.
However, the grindability and energy density of the biomass char showed great improvement. A kinetic study on the generation of
the main non-condensable gases was undertaken and we conclude that the gases are formed by parallel independent first-order
reactions. Characteristic kinetic parameters for the generation of each gas were determined.
agricultural biomass, torrefaction, pretreatment, grindability, kinetics
Citation:

Wang G J, Luo Y H, Deng J, et al. Pretreatment of biomass by torrefaction. Chinese Sci Bull, 2011, 56: 14421448, doi: 10.1007/s11434-010-4143-y

As a source of green energy, biomass generates less SO2

and NOx, and the emission of other gases is negligible and
importantly it is CO2 neutral. However, biomass has some
drawbacks such as high moisture content, hydroscopic nature, low energy density, difficult for storage, production
dependent on seasonal variation and wide distribution [1,2],
which makes it unsuitable for large-scale use. Therefore,
plenty of research has focused on the conversion of
low-grade biomass into high quality energy. Torrefaction is
an effective chemical pretreatment to deal with biomass.
After torrefaction, the solid biomass products have a smaller
volume and higher energy density than untreated biomass
and, therefore, the cost of storage and transportation can be
reduced. If the solid products are pressed into briquettes
their energy density can be further enhanced. With increased grindability of the solid products that compose the
biomass, this fuel may be used on large scale in a pulverized
*Corresponding author (email: yhluo@sjtu.edu.cn)
The Author(s) 2011. This article is published with open access at Springerlink.com

boiler or an entrained flow gasifier [3].

Torrefaction is a mild pyrolysis treatment that involves
heating the biomass at moderate temperatures between
200C and 300C under an inert atmosphere. During this
process, most of the water and some light volatiles are removed from the biomass. Prins et al. [46] undertook
comprehensive studies on pyrolysis kinetics and characteristics of the pyrolysis products of willow, straw and larch
using thermogravimetry and a semi-industrial scale bench at
230300C. Saravanakumar et al. [7] studied the conversion
of wood by pyrolysis to charcoal in a partial combustion
kiln (under different conditions) to understand the influence
of moisture content, type and size during charcoal generation, the main reactions at different temperature and the
characteristics of carbocoal. Felfli et al. [8] studied the torrefaction of wood briquettes from 220270C and their results show that the solid products have good hydrophobicity.
According to the energy yield, the most suitable temperature for torrefaction was found to be between 250 and
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Wang G J, et al.

Chinese Sci Bull

270C. Finally, a technical and economic feasibility analysis about the torrefaction of wood briquettes under Brazilian
national conditions has been reported [9]. Arias studied the
grindability and reactivity of the solid products of wood
torrefaction from 240280C and compared them to raw
materials, and kinetic parameters were calculated [1]. Jiang
et al. [10] studied the effects of temperature and residence
time on the solid state products calorific value, quality and
energy yield after torrefaction of a wood block, sawdust and
a rice husk extrusion bar. Their results show that torrefaction is optimum at a temperature of 280C. Zhang et al. [2]
studied the effect of rice straw torrefaction at 300550C on
the quality of the resultant semi-coke and the energy yield.
Entrained flow gasification results for biomass and charcoal
were compared based on ASPEN PLUS software and the
results show that entrained flow gasification is ideal at a
torrefaction temperature of 400C. To find a relationship
between biomass torrefaction and energy density, grindability and overall gasification efficiency, Zhao et al. [11] carried out torrefaction experiments in a lab-scale reactor with
four kinds of biomass (rice husk, Korean pine, pinus sylvestris, ashtree) as a feedstock between 230C and 290C.
Their results show that at a torrefaction temperature of
250C the torrefied biomass has a better mass and energy
yield.
Agricultural biomass is different to woody biomass because crops have a higher hemicellulose content that decomposes more easily when heated. We conducted torrefaction experiments in a fixed bed reactor with cotton stalk and
wheat straw at 200C, 250C and 300C to determine the
distribution of the pyrolysis products. We were especially
interested in the pattern of gas release, which made up about
60% of the total volatile products. By comparing the particle distribution of solid products and raw biomass that were
ground under the same conditions, it is found that the torrefied biomass had better grindability. At higher temperature,
the energy yield of cotton stalk reduced dramatically but
wheat straw showed a moderate trend. A kinetic analysis of
CO2 and CO generation from cotton stalk and wheat straw
showed that they have a similar CO generation activation
energy while the CO2 generation activation energy of wheat
straw is far higher than that of cotton stalk.

1 Experimental
1.1

Materials

Two kinds of typical agricultural biomass (cotton stalk

Table 1

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May (2011) Vol.56 No.14

and wheat straw) were collected from Wuwei County in

Anhui Province. The raw material was cut into pieces to
give an average length of 25 mm. It was then dried using an
air-blower-driver drying closet at 95C over about 24 h and
the material was stored in sealed bags. The proximate and
ultimate analysis of the cotton stalk and wheat straw is
listed in Table 1.
1.2

Experimental equipment and procedures

The pyrolysis experiments were carried out in a vertical

fixed bed furnace (Figure 1). An alundum tube with a diameter of 60 mm and a length of 500 mm was used. Silicon
carbide rods with a length of 200 mm were arranged in the
middle of the alundum tube for heating. Samples were
placed on a grate, which was 200 mm above the bottom of
the alundum tube. Two thermocouples 150 mm apart were
arranged outside the tube for temperature measurement and
automatic control. As a protective gas, nitrogen was piped
from the bottom of alundum tube and then carried the reaction products out of the pyrolysis zone through the grate and
discharged them out of the stainless steel outlet pipe on top
of the fixed bed furnace. The outlet pipe was fitted with a
heating device to ensure that the temperature was no less
than 200C to prevent tar and other liquid products from
condensing before entering the condensation unit. Condensable volatiles were trapped by a two-mouth flask immersed in liquid nitrogen. After filtration, small particles
and not condensed gases passed into an infrared multi-gas
analyzer, Gasboard-5 (Wuhan Sifang). The analyzer showed
a real-time display of the percentage of CO, CO2, H2, CH4,
O2 and the data was automatically recorded and saved by a
computer. The raw biomass and torrefied samples were
ground using a Corey KER-1/100A sealed pulverizer and
then screened with a sieve for weighing. The calorific value
of the charcoal was measured using an intelligent calorimeter (Hebi Huatong ZDHW-6 type).
Samples of 220.1 g were taken from the grate and then
the joints of entrance and exit of the furnace was sealed by
high-temperature resistance glue. A high flow of high-purity
nitrogen gas was then used to purge the bottom of the furnace to remove any air from the alundum tube. When the
concentration of oxygen dropped to 0.5%, the gas inlet
valve was regulated to ensure the flow of nitrogen gas was
maintained at 500 mL/min. The heating device was then
turned on and the samples were heated from room temperature to the target temperature of 100C at a heating rate of
30C/min and kept at this temperature for 10 min. The
thermocouples recorded the heating area temperature. The

Proximate and ultimate analysis of the investigated biomass (ad)

Sample

Cotton stalk
Wheat straw

M
1.19
3.30

Proximate analysis (%)

V
FC
76.92
19.19
71.59
18.73

A
2.70
6.38

LHV (MJ kg1)

19.32
17.81

C
46.43
43.00

Ultimate analysis (%)

H
O
N
6.18
42.62
0.80
5.36
41.11
0.63

S
0.08
0.22

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Wang G J, et al.

Figure 1

Chinese Sci Bull

Fixed bed reactor.

final temperatures were set to either 200C, 230C, 250C,

270C or 300C (we only obtained the solid product yield
and HHV measurements) at the same heating rate and the
samples were kept at this temperature for 30 min. Finally,
the heating device was turned off but the nitrogen gas was
maintained until the furnace temperature was below 110C
upon which the sample was removed. The solid and liquid
products were then weighed. This experiment was repeated
three times for each sample and the average value of the
three experiments is reported. Each sample was ground for
5 min and then they were passed through three different size
sieves (100 m, 150 m, 450 m) for screening and weighing.
To determine the total volatiles ratio at specific temperatures, we also conducted experiments at corresponding
temperatures until the gas concentration was less than 0.1%.

2
2.1

Results and analysis

Product distribution

After torrefaction at 200C, 250C and 300C, the products

contained solid charcoal, a liquid ingredient (water and tar)
and gases (mainly CO2 and CO). The weight percentage of
the torrefaction products is shown in Table 2. The sum of
the liquid and gas products corresponds to the weight loss
through torrefaction, and this is known as biomass conversion efficiency. The conversion efficiency indicates the effect of the torrefaction process on the raw materials. It is
related to the size of the raw biomass and the torrefaction
conditions. As the torrefaction temperature increased, the
conversion rate of the two samples also increased. The yield
of solid product decreased but the yield of liquid and gas
components increased. During biomass pyrolysis, hemicellulose decomposes between 200C and 250C and cellulose
decomposes between 240C and 350C while lignin decomposes between 280C and 500C and over longer time

May (2011) Vol.56 No.14

[12]. The biomass pyrolysis products are closely related to

temperature and heating rate. At higher temperatures, more
gas is produced because of secondary reactions and tar decomposition but slow pyrolysis favors the formation of solid
coke while fast pyrolysis increases the tar yield. The
mechanism of biomass pyrolysis is shown in Figure 2.
The torrefaction of biomass is mainly composed of
hemicellulose pyrolysis with a partial decomposition of
cellulose and lignin. Between 200C and 300C xylan
hemicellulose undergoes dehydration, dehydroxylation and
deacetylation reactions. Hemicellulose thermal decomposition products are mainly gases and liquids [5] and at lower
temperatures dehydration reactions has a major role in the
release of volatiles and the formation of solid products. At
higher temperatures, the decomposition of L-glucan will
have a major role. The increase in water content results
from water evaporation from the sample and also from the
dehydration of organic molecules. After torrefaction, the
stalk will have lost most of its water while some low molecular weight volatile organic compounds and long-chain
polysaccharides decompose. Lignin pyrolysis produces
mainly charcoal [13].
At higher temperature, the solid products gradually
change color from brown to black and the apparent volume
reduces significantly. Additionally, the solid products become brittle, fragile and cylindrical or spherical in shape.
As the solid products lose most of their moisture and their
volatile matter, their energy density increases and the charcoal even has a hydrophobic character [5,8,13].
The brown liquid products have an irritating smell and
this is mainly composed of water, acetic acid and a small
amount of methanol, lactic acid and furfural. [5,13]. As the
pyrolysis temperature increases, the liquid product yield
increases and it has a darker color. The liquid mainly comes
from the decomposition of hemicellulose [11] and the liquid
product yield is very small at 200C of which water accounts for a large proportion. Water is released in the form
of evaporation (mainly below 150C) followed by dehydraTable 2
Sample
Cotton
stalk
Wheat
straw

Distribution of the torrefied biomass products

Temperature Solid yield Liquid yield Gas yield
(C)
(wt%)
(wt%)
(wt%)
200
63.89
4.14
31.97
250
33.8
13.8
52.4
300
30.04
17.28
52.68
200
47.56
3.93
48.51
250
41.24
9.69
49.07
300
31.61
11.57
56.82

Figure 2

Mechanism of biomass pyrolysis.

Conversion
(%)
36.11
66.2
69.96
52.44
58.76
68.39

Wang G J, et al.

Figure 3

Chinese Sci Bull

Grindability of the original straw and char. (a) Cotton stalk, (b) wheat straw.

tion and depolymerization. As the temperature increases to

250C and 300C, the hydroxyl groups in hemicellulose
easily form intra- and intermolecular hydrogen bonds to
eventually form water. Simultaneous decarboxylation, glycosidic bond breaking, C-O bond breaking, C-C bond
breaking and the formation of a series of acids, alcohols,
aldehydes, ethers such as tar substances, and CO, CO2, CH4
and other gas compounds have been reported [14].
2.2

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May (2011) Vol.56 No.14

Grindability and energy yield

The grindability of the raw biomass and torrefied biomass is

shown in Figure 3. After milling, about 80% of the raw
biomass particles had diameters larger than 450 m and
about 10% were smaller than 150 m. After torrefaction,
the grindability of the solid products improved greatly. After torrefied at 200C, 70% of the solid products were larger
than 450 m and 20% were smaller than 150 m. When
torrefied at 250C, 30% of the ground particles were larger
than 450 m while 40% of the particles were smaller than
150 m. The grindability of the solid product torrefied at
300C almost has the same characteristics as that torrefied
at 250C.
Torrefaction has a large effect on the strength of the cell
wall in biomass material. The microfibrils which aggregate
into very long strands by polysaccharides are enclosed in a
continuous system of amorphous lignin. By decomposing
hemicellulose in the torrefaction process, the orientation of
the microfibrils in the lignin matrix may change, which influences the viscoelastic properties of the biomass [6]. Arias
[1] investigated raw biomass and torrefied biomass by optical microscopy and found that after pyrolysis, the fibers
between the biomass particles were broken and the decrease
in biomass particle size is mainly because of the reduction
in length and the change to spherical geometry.
After torrefaction, the physical form of the biomass
charcoal changed as it reduced significantly in size, the
color became dark brown or black and the weight decreased.

The carbon content increases and the oxygen as well as the

hydrogen content decreases in the charcoal because the
process of pyrolysis releases water, CO2 and other volatile
matter; therefore, the calorific value of the charcoal
increases significantly [2]. The HHV of charcoal is shown
in Table 3. Under the same conditions, the calorific value of
wheat straw charcoal was increased but the value was lower
than which of cotton stalk charcoal that mainly because
wheat straw has a higher ash content than cotton stalk.
The energy density is reflected in the energy per unit
charcoal which results from torrefaction. The weight loss
during the process also needs to be considered. The energy
yield reflects the magnitude of energy conversion of the
biomass during the torrefaction process. This will be beneficial for a reasonable assessment of the pretreatment process. The energy yield was calculated as follows:
yenergy =

mchar HHVchar
100%,
m0 HHV0

(1)

where m is the weight, HHV0 and HHVchar are the calorific

values of the original straw and the charcoal, respectively.
The energy yield of the solid charcoal is shown in Figure 4.
Both kinds of biomass generally have a high energy yield at
200C. At higher temperatures, the energy yield decreases.
As the pyrolysis temperature increases from 200C to
230C and to 250C, the energy yield of cotton stalk deTable 3

Proximate analysis of the solid product

Sample-temperature
(C)

M (%)

Cotton stalk -200

Cotton stalk -250

A (%)

HHV
(MJ kg1)

41.89

8.44

23.94

44.48

12.69

24.57

V(%)

FC (%)

5.24

44.43

6.7

36.13

Cotton stalk -300

6.1

31.16

48.0

14.74

25.03

Wheat straw -200

6.51

39.01

38.98

15.5

19.84

Wheat straw -250

4.83

28.21

43.66

23.3

20.85

Wheat straw -300

4.78

14.84

55.43

24.95

21.67

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May (2011) Vol.56 No.14

tion of oxygen-containing gas.

The dehydration and dehydroxylation reactions of hemicellulose resulting in water and CO2 makes up a large part
of the volatile products so the O/C ratio of charcoal is
greatly reduced. A lower O/C ratio indicates a higher gasification efficiency. Because of water removal as well as
CO2 and CO gas release, the C/O ratio of charcoal increases
and the energy density of charcoal improves [8].
(ii) Gas generation kinetic parameters. For the torrefaction process, gas generation is considered to be a group of
independent first reactions and every gas has its own activation energy. Encinar [15] have described this in detail. We
used a similar formula and eq. (2) describes how the gas
content (moles) changes with time.
Figure 4

Energy yield of solid charcoal under different temperature.

creases rapidly from 79% to 47% and to 42%, respectively.

At 270C and 300C, the percentage decreases slightly to
40.3% and 38.9%, respectively. The energy yield of the
wheat straw did not change as dramatic as that of the cotton stalk. The energy yield for the five examined operating
conditions were: 53%, 50.1%, 48.3%, 43% and 38.5%. At
250C, the main reaction is hemicellulose pyrolysis [1].
Compared with wood biomass under similar conditions
[10,11] the energy yield of the agricultural biomass is substantially lower because agriculture biomass has higher
hemicellulose content than wood biomass. The results
show that a higher torrefaction temperature results in a
lower energy yield. To obtain a higher energy yield for
agricultural biomass the temperature should not exceed
250C.
2.3

Generation law for gas products

(i) Gas products. The gas products formed are mainly CO2,
CO, small amounts of CH4 and even traces of H2. The gas
mainly comes from the decomposition of hemicellulose
[5,14], combined water release between 100180C and the
generation of CO, CO2 and condensable volatiles between
180C and 270C [7]. A law for the gas products for the two
samples under different conditions is shown in Figure 5.
The concentration of the gas components follows the order:
CO2, CO, CH4 and with the pyrolysis temperature increases
the gas concentration and the cumulative amount of released
gas for both wheat straw and cotton stalk ware increased.
Gas release occurred earlier in the reaction for cotton stalk
than for wheat straw and the gas yield of cotton stalk was
larger. This is because the volatile content of cotton stalk
(76.92%) is higher than that of wheat straw (71.59%). Xylan hemicellulose begins to pyrolyze at about 200C while
lignin and cellulose start pyrolysis at about 250C. At lower
temperatures, the generation of CO, CO2 and H2O is because of hemicellulose and cellulose decomposition while
dehydroxylation (-COOH) has a crucial role in the produc-

m0
ln
= k t,
m0 m

(2)

where m0 represents the total gas content that has been generated after all possible pyrolysis of the residue has been
completed, that is, when the residue is exhausted. m and k
represents the number of moles generated and the gas generation rate constant at time t, respectively. Because the
CH4 concentration is very small, the total amount produced
is very low and the calculation of CH4 generated kinetic
parameters is not required. Results of the CO and CO2
generation dynamic analysis are shown in Table 4.
The Arrhenius equation (eq. (3)) can then be used to determine the activation energy (Ea) and the results are shown
in Table 5. Wheat straw and cotton stalk have similar activation energies for CO generation. The CO2 generation activation energy of wheat straw is slightly higher than that
for the CO2 generation activation energy of cotton stalk.
The activation energy indicates the degree of difficulty for a
reaction to occur and the effects of temperature on the reaction rate. Larger activation energies indicate more difficult
reactions and less temperature sensitivity.
ln k = ln k0

Ea 1
,
R T

(3)

where k0, Ea, R, T represent the pre-exponential factor

(min1), activation energy (J mol1), gas constant and temperature (K), respectively.

Conclusions

After torrefaction the products of cotton stalk and wheat

straw are mainly solid products (charcoal), liquid products
(water and tar) and gas products (mainly CO2 and CO).
With an increase in the torrefaction temperature, the quality
yield of charcoal decreases significantly, the energy density
increases and the energy yield decreases. The yield of liquid
products and gas products increase as the temperature increases because of the decomposition of hemicellulose. The

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May (2011) Vol.56 No.14

1447

Figure 5 Concentration changes of gases during torrefaction. (a) Cotton stalk 200C; (b) cotton stalk 250C; (c) cotton stalk 300C; (d) wheat straw 200C;
(e) wheat straw 250C; (f) wheat straw 300C.
Table 4

Rate constant of gas generation during biomass torrefaction

Sample

Cotton stalk

Wheat straw

Temperature
(C)
200
250
300
200
250
300

K (103 min1)
CO
48.68
71.18
73.09
128.49
178.48
192.65

CO2
31.60
33.03
35.14
141.72
178.66
183.56

apparent volume of the solid products decreases significantly and their grindability improves greatly with an increase in temperature. This reduces the cost of storage and

Table 5 Kinetic parameters of CO2 and CO generation during biomass

torrefaction
Sample

Gas

Cotton
stalk

CO2
CO
CO2
CO

Wheat
straw

Activation energy Pre-exponential Correlation coefficient (R2)

Ea (kJ mol1)
factor k0 (min1)
2.37
0.058
0.989
9.38
0.555
0.917
5.96
311.03
0.931
9.27
1.405
0.958

transportation and also helps to reduce the required milling

energy. Biomass torrefaction can be used as a pretreatment
technology for briquettes, co-combustion with coal in boiler
or co-gasification in an entrained flow gasifier. This method
can improve the characteristics of the biomass therefore

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Wang G J, et al.

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large-scale use of biomass can become feasible. Taking into

account the energy yield, grindability and other factors, the
experiment results reveal that the optimum torrefaction
temperature is between 230C and 250C, and the reaction
time should be around 30 min.

May (2011) Vol.56 No.14

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