J Therm Anal Calorim (2015) 120:317–323
DOI 10.1007/s10973-014-3914-0
Gasification of selected woody plants
Buryan Petr
Received: 30 July 2013 / Accepted: 3 June 2014 / Published online: 8 July 2014
 Akadémiai Kiadó, Budapest, Hungary 2014
Abstract The article contains laboratory data comparing
the rate of gasification of five types of woody plants—
beech, oak, willow, poplar and rose. The gasification rate
was determined thermogravimetrically. Carbon dioxide
and steam were used as gasification gases. Willow wood
was the most gasifiable, whereas rose wood the least.
Keywords Biomass gasification  TG  Water-steam
Introduction
Gasification is a process which comprises a series of
interconnected component actions, such as drying, pyro-
lysis, incineration and gasification itself. To a certain
degree, these processes may occur separately in various
parts of the reaction space or in one reaction space [1].
Biomass in generator gasification is exposed to numer-
ous effects, targeted for the creation of gas containing
mainly CO2, CO, H2, N2, water steam, hydrocarbons, etc.
On the other hand, the products include also a less desir-
able solid residue, containing besides ash also a part of
non-gasified biomass.
Biomass gasification includes, besides the heteroge-
neous and homogeneous oxidation–combustion reactions
connected with heat generation, several steps that are listed
below [1–4]:
• biomass heating and water vaporisation,
B. Petr (&)
Department of Gas, Coke and Air Protection, Institute of
Chemical Technology Prague, 166 28 Prague 6, Czech Republic
e-mail: buryan.petr@seznam.cz; buryanp@vscht.cz
• biomass pyrolysis (degasification), releasing various
organic substances (hydrocarbons and tar) and water,
sometimes also hydrogen sulphide and ammonia,
• a reaction of solid carbonaceous residue with water
steam and carbon dioxide within heterogeneous reac-
tions,
C þ CO2 ! 2CO
C þ H2 O ! CO þ H2
2C þ 2H2 O ! 2CO þ CH4
• numerous other reactions between the solid and gas
phases, or more specifically occur only in the gas phase,
such as the reaction between hydrocarbons and water
steam:
C þ H2 O ! 2CO
Cn Hm þ H2 O ! ðn þ m  ð1=2ÞÞH2 þ nCO
• an inseparable parts are the reactions of hydrogen with
the solid phase, conversion reactions and the methana-
tion of the primarily created gaseous elements.
The main aim of the research was to obtain supporting
materials which can be used for the selection of biomass
for the newly built cogeneration unit in which gas obtained
from the biomass will be combusted.
The composition of the emerging gas depends both on
the thermodynamic conditions of the process (temperature,
pressure and gasification ratio) and on the generator type,
biomass dwell time in it or biomass properties [5–7]. In
comparison with coal, biomass has a higher volatile-com-
bustible content, which leads to increased reactivity. It,
however, has a lower ash content with a lower melting
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318
point. This allows for gasification at lower temperatures
[7, 8].
For the assessment of gasification, such processes or
reactions are decisive whose rate is the slowest. From the
mentioned processes during biomass gasification, these are
definitely the reactions between the carbon of the solid
residue after the pyrolysis and the gaseous components, i.e.
carbon dioxide and water steam [1]. For the assessment of
the gasifiability of selected woody-plant samples, the
measurement of the rate of gasification of their carbona-
ceous residue in the reaction with carbon dioxide, or with
water steam, was, therefore, used, namely in dependence
on the temperature, because the temperature is another
decisive parameter affecting gasification rate [1].
Gasification rate r is monitored by means of changes in
the mass of the sample studied in time and thus has a
dimension [mg min-1]. For the quantitative expression of
gasification rate, it is possible to use the values of instan-
taneous gasification rate R, defined as the mass loss related
to the instantaneous sample mass [mg mg-1 min-1].
Nevertheless, the mass loss at a given instant is most fre-
quently related to the initial mass of the sample, in which
case the rate is labelled as R0—[mg mg-1 min-1].
For a comparison of the gasifiability at a given tem-
perature, it is also possible to utilise a graphic comparison
of the gasification curves of various samples or to compare
the R0 values with respect to a given conversion value. This
work has used a comparison of R0 values when a 95 %
conversion was attained.
The gasification process in a number of cases is affected
by the presence of catalytic materials concentrating during
degasification mainly on the surface of the solid carbona-
ceous residue. It arises from the numerous statements
summarised in [5–9] that rinsing the pyrolysis residue with
water affects the rate of gasification, using CO2 and H2O
only a little, because water removes only the water-soluble
inorganic materials. The application of acid extraction
solutions dissolving inherently bound cations in carboxyl
and hydroxyl groups slows the gasification rate.
Sakawa [10] proposed for the expression of the catalytic
effects of the inherent inorganic components of coal the so-
called alkalinity (basicity) index:
Fe2 O3 þ CaO þ MgO þ Na2 O þ K2 0
B= A
SiO2 þ Al2 O3
where A is the ash mass [mass%],
MexOy is the mass of the individual oxides, [mass%]
and has shown that there is a good correlation between
gasification reactivity and the alkalinity index including the
effect of water rinsing of pyrolysis of the carbonaceous
residue.
The above-mentioned alkalinity index corresponds to
the relations evaluating the determination of coal and coke-
123
B. Petr
ash fusibility [11] characterisable, e.g. by the basicity/
alkalinity ratio or silicate ratio.
Experimental
Equipment for gasification rate determination
Since gasification is a heterogeneous reaction between the
solid (carbon from the biomass after pyrolysis-degasifica-
tion) and gaseous phases (carbon dioxide and water steam)
[1, 4], the most suitable comparative analytical equipment
seems to be thermobalance, which monitors carbon-mass
loss in dependence on the reaction time at a selected
temperature. The construction of the thermobalance
applied can be seen in Fig. 1.
The basic element of the thermobalance constructed is a
quartz spiral, vertically hung in the thermobalance body (1)
and reactor (8); at the end of the spiral, there is a small pot
(9), into which the biomass sample being gasified is placed.
On the spiral, there is a screen (3), which along with two
light-emitting diodes (4) and two photodiodes (5) forms a
position detector. Without further equipment, the position
of the screen would change as a consequence of the sample
mass change during the gasification, which is, however,
prevented by the solenoid (6), holding the screen and with
it also the sample in the same position. With the sample
mass change, however, also the value of the electric current
flowing through the solenoid must change. The change of
the electric-current intensity is, hence, directly proportional
to the mass loss, which is scanned and registered by a
recording unit.
The apparatus for the gasification by carbon dioxide
The main parts of the apparatus for the monitoring of the
gasification by carbon dioxide consist of a quartz-glass
reactor (5), regulated electric furnace (7) and a thermo-
balance (5). The apparatus scheme is shown in Fig. 2. The
apparatus includes pressure vessel (1) with model gas. The
pressure vessel is followed by a manostat (2) to maintain a
constant pressure of both the gases, two needle valves (4)
to set their constant through flow and two rotameters (3) to
measure their through flow. It is possible to induct either
rinsing gas (nitrogen) or gasification gas (carbon dioxide
with nitrogen) to the reactor (6). The gasification gas
contained 23.5 vol% of carbon dioxide in nitrogen. The
nitrogen for purging the apparatus. The nitrogen for rinsing
the apparatus is led from above through the thermobalance
and model gas to the upper part of the reactor. The mass
loss is read by a measuring device (12) and registered by a
recorder (13). The temperature in the reactor is measured
by a thermocouple (8).
Gasification of selected woody plants 319

Fig. 1 Thermobalance scheme

1 the glass casing, 2 a quartz- 11
glass spiral, 3 a screen, 4 a light- 1
emitting diode, 5 photodiode, 6
solenoid, 7 the solenoid’s metal 1– the glass casing,
core, 8 the quartz casing of the 2 2 – a quartz-glass spiral,
reactor, 9 sample basket, 10 3 – a screen,
thermocouple, 11 purging-gas 4 – a light-emitting diode,
inlet, 12 the inlet of the 5 – photodiode,
gasification gas into the reactor, 5 4 6 – solenoid,
13 gas off take from the reactor 7 – the solenoid’s metal core,
3 8 – the quartz casing of the reactor,
9 – sample basket,
10 – thermocouple,
6 11 – purging-gas inlet,
12 – the inlet of the gasification gas into the
7 reactor,
13 – gas off takefrom the reactor
12 13

10

4 3 4 3
10 5 10 5
9 12 13 9 12 13
11 11
4´ 3´ 6 4´ 3´ 6 7
7
15
1 2 1 2
8 14 8

Fig. 2 The scheme of the apparatus for measuring the gasification by
carbon dioxide 1 a pressure bottle with model gasification gas (carbon
dioxide with nitrogen), 2 manostat, 3 30 rotameters, 4 40 needle valves,
5 thermobalance, 6 a quartz reactor, 7 a regulated electric furnace, 8
thermocouple, 9 photodiodes, 10 light-emitting diodes, 11 solenoid,
12 a measuring device, 13 recorder
Fig. 3 The scheme of the apparatus for measuring water-steam
gasification 1 a pressure bottle with model gasification gas (nitrogen),
2 manostat, 3 30 rotameters, 4 40 needle valves, 5 thermobalance, 6 a
quartz reactor, 7 a regulated electric furnace, 8 thermocouple, 9
photodiodes, 10 light-emitting diodes, 11 solenoid, 12 a measuring
device, 13 recorder, 14 thermostat, 15 a water-steam saturator

The apparatus for the gasification by water steam

This apparatus is almost identical with the apparatus for
gasification by carbon dioxide, but with the difference
that it additionally contains a water-steam saturator (15),
which is placed in the thermostat (14). Besides that, the
pressure bottle (1) contains nitrogen. The model gas is
thus the mixture of nitrogen and water steam. The water-
steam content in 1 m3 of nitrogen corresponded at the
time of the measurement to the value of 83.02 mg m-3
(Fig. 3).

123
320 B. Petr

Table 1 Elemental composition, gross calorific value, ash content and the amount of the carbonaceous residue after heating to 900 C—data
related to dry mass of wood without bark
Woody plant C/mass% H/mass% N/mass% S/mass% Q/MJ kg-1 Carbonaceous residue/mass% Ash/mass%

Rose 0.06 47.28 5.78 - 18.9 20.10 1.28

Beech 0.16 49.35 6.00 - 18.8 18.51 1.29
Oak 0.16 48.90 5.71 - 18.7 16.99 1.74
Poplar 0.30 48.76 6.09 - 18.7 15.14 1.11
Willow 0.18 48.85 5.95 - 18.4 15.07 1.32

Table 2 Ash composition—mass % 100

90

Mass loss/mass % min–1

Oxide/woody Oak Poplar Willow Rose Beech 80
Beech
plant Rose
70
Willow
Na2O 0.240 0.977 0.750 3.250 0.450 60
Oak
50
MgO 7.660 5.540 7.930 16.810 5.810 Poplar
40
Al2O3 0.193 0.076 0.347 0.064 0.093
30
SiO2 0.251 0.343 0.420 0.735 1.900 20
P2O5 5.030 16.220 9.970 21.240 20.330 10
SO3 1.310 2.740 2.720 5.520 1.910 0
0 10 20 30 40 50
K2O 10.710 15.300 23.970 15.370 24.610
Time/min
CaO 71.070 58.060 51.120 36.400 43.450
TiO2 0.012 0.007 0.043 0.009 Fig. 4 The dependence of the mass loss of solid pyrolysis residue
MnO 1.680 0.061 0.648 0.063 0.627 during the carbon dioxide gasification of the woody-plant samples at a
Fe2O3 0.319 0.104 0.499 0.038 0.223 temperature of 870 C
NiO 0.003 0.007 0.010
100
CuO 0.032 0.063 0.038 0.058 0.043
90
ZnO 0.131 0.204 1.100 0.118 0.098
Mass loss/mass % min–1

SrO 0.296 0.201 0.220 0.280 0.118 80

Beech
BaO 1.030 0.203 0.290 70
Rose
PbO 0.010 0.020 0.020 0.043 0.020 60
Willow
Norm 84.70 86.20 85.60 65.50 90.40 50
B 145.03 211.88 115.13 352.70 48.25 40 Oak

Norm…Sum. conc’s before normalisation to 100 %, B.alkalinity 30 Poplar

(basicity) index 20

10

The monitored materials
The rate of gasification was measured for five woody
plants—poplar, willow, oak, beech and rose. Since it arises
from the rules of thermodynamics that what is decisive for
the assessment of the overall gasification rate is the rate of
the slowest process, the study was conducted for the car-
bonaceous residue after pyrolysis (degasification) [3]. The
residue had been acquired through the heat treatment of the
raw materials monitored in vacuo in an inert nitrogen
atmosphere at a temperature of 900 C for 60 min. The
amount of the carbonaceous residue acquired from the
studied woody plants desiccated at 105 C and the ash
content in dry woody plant are listed in Table 1. Its com-
position obtained by means of an XRF analysis is
0
0 10 20 30 40
Time/min
Fig. 5 The dependence of the mass loss pyrolysis residue during the
water-steam gasification of the woody-plant samples at a temperature
of 870 C
summarised in Table 2 (ARL 9400 XP? spectrometer
equipped with an X-ray lamp with an Rh-anode and Be
front window as well as with a source X-ray lamp with a
maximum wattage of 3.6 kW; fully automatic goniometer
with a 4-position primary-collimator changer and a
9-position crystal changer, which is equipped with 6 plane
crystals—LiF200, LiF220, Ge111, PET, TLAP and AX20).
Elemental analysis was performed using the device
Thermo Scientific Flash 1112, which is constructed as an

123
Gasification of selected woody plants 321

Table 3 The order of the woody plants by R0max in carbon dioxide gasification/g g-1 min-1
Woody plant Temperature/C Woody plant Temperature/C Woody plant Temperature/C
800 820 870

Rose 0.726 Rose 0.862 Oak 2.120

Poplar 0.743 Oak 0.945 Rose 2.295
Oak 1.016 Beech 1.123 Beech 2.646
Beech 1.071 Poplar 1.263 Poplar 2.792
Willow 1.420 Willow 2.093 Willow 3.397

Table 4 The order of the woody plants by R0max in water-steam gasification/g g-1 min-1
Woody plant Temperature/C Woody plant Temperature/C Woody plant Temperature/C
800 820 870

Rose 1.171 Rose 1.328 Rose 1.910

Oak 1.916 Oak 2.173 Oak 2.112
Poplar 2.099 Poplar 2.210 Beech 2.980
Beech 2.323 Beech 2.735 Poplar 3.964
Willow 3.511 Willow 3.202 Willow 4.646

apparatus for determining the representation of carbon,
hydrogen, nitrogen and sulphur combustible. Dumas
chromatography was used to determine the results.
Surface of the studied pyrolysis residues was investi-
gated by nitrogen adsorption at the boiling temperature of
liquid nitrogen using a device Coulter SA 3100. Before
measurement, the sample surface was degassed by vacuum
and heated to temperature of 150 C for 2–4 h. The surface
of the tested samples was calculated by BET equation
(Brunauer–Emmett–Teller). Determination of the gross
calorific value (Q) was carried out by calorimeter IKA
C200 [12].
Results and discussion
After the sample of solid pyrolysis residue reached the
thermobalance at room temperature, the inner space of the
thermobalance and of the reactor was purged with nitrogen
for full deoxidation. The reactor was subsequently heated to
the desired temperature. After it was attained, gasification
gas was let into the reactor (a through flow of 2 l min-1.),
after which the mass loss of the sample, resulting from the
gasification reaction, was continuously recorded.
Mass-loss rate at 800, 820 and 870 C was measured
for each solid pyrolysis residue sample both through a
reaction with carbon dioxide and with water steam. The
examples of a synoptic comparison of the acquired curves
of the mass loss during the carbon dioxide gasification of
the individual woody plants (23.5 vol% of CO2, 76.5 vol%
of N2 and 0.4 vol% of O2) and water steam (83.02 mg m-3
in nitrogen) at the highest applicable temperature are
shown in Figs. 4 and 5.
The findings point out that the rate of gasification by
carbon dioxide is lower than the rate of gasification by
water steam. E.g. steam gasification of 50 % mass loss for
poplar and willow has already been achieved in around
10 min, while CO2 gassing occurred in about 18–19 min.
Overall steam gasification of willow occurred at about
17 min, and poplar at 21 min. During gasification with
carbon dioxide, this condition occurred in approximately
30 min. Overall gasification of rose solid pyrolysis product
by steam occurred in 38 min, and carbon dioxide occurred
in approximately 43 min. Full gasification by carbon
dioxide and water stem of solid products of oak and beech
pyrolysis occurred after the same period of time—after ca
37 min.
The quantitative expression of the reaction rate R0
through an instantaneous mass loss related to the initial
sample mass [3] with respect to the changes on the surface
of the matrix being gasified varies in the course of the
experiment. In some cases, this change is rather negligible,
while in others the rate-value change is more significant,
especially if the average rate of the reaction is lower. This
concerns mainly lower temperatures. In these cases, char-
acteristic rates related to a specific point are used. It may be
the mean rate in time corresponding to the selected mass
loss (e.g. t40, t60) or the rate during the conversion corre-
sponding to the highest rate attained. As arises from the
curves presented, this rate is the highest approximately at a
95 % conversion. The rate values in Tables 3 and 4 were,
therefore, calculated for the 95 % conversion, and are

123
322 B. Petr

250 wood (compiled in Tables 3, 4) show that we could not

demonstrate significant correlation between the gassed
200
matrices reactivity and either the catalytic effects of
Specific surface/m2 g–1

inherent inorganic components (expressed in absolute

150
100
50
0 (from Beckman company).
Willow Poplar Beech Rose
Fig. 6 A comparison of the specific surface of pyrolysis residue
labelled as R0max. The calculation was based on interlaying
the dependence of the sample mass loss in time for various
temperatures by a polynomial trend line of the second order
for a 95 % conversion and the subsequent derivations of
the equation were acquired.
Mass transfer in the gas film at the surface of solid
particles describing heterogeneous catalysed and uncatal-
ysed reaction is a function of many parameters. One
example is the mass velocity of gas, particle size and
physical properties of the hydrodynamic generated and
gasificating gas and also the number and size of individual
voids and the total surface area of particles gassed.
Therefore, in this work, we aim to compare this parameter
of studied materials usable in the choice of materials for
technological objectives, such as cogeneration including
gasification of biomass.
Data in Table 2 on the composition of the ash and the
order of reactivity studied the pyrolysis products of solid
content of selected metals, e.g. potassium or total con-
centration of alkali metals, etc.) or alkalinity index B by
Sakawa [10].
Therefore, when interpreting the order of the reactivities
of the individual samples monitored, we focused first of all
on determining specific surface and pore distribution. The
specific surface, pore volume and pore distribution were
measured by the BET method using a Coulter SA 3110
Oak The measurement results summarised in Fig. 6, showing
the specific surfaces of the samples monitored, do not
correspond to the determined order of the reactivities listed
in Tables 3 and 4, because reactivity in general should
increase with the growing specific surface. However, we
acquired a general answer by comparing the pore distri-
bution, mainly for the area of 20–80 nm—see Fig. 7. It is
evident from this figure that the most reactive samples of
such gasified substances as willow and poplar had the
greatest share of pores in the area of 20–80 nm, while less
reactive samples had the greatest share of pores in the area
\6 nm.
The knowledge gained here evidences that diffusion
gasifying gas components from the main gas stream border
film to the surface of solid particles, as well as the fol-
lowing reaction of gas with the solid on the surface and
also the diffusion of reaction products from the surface of
the solid film of gas back into the bulk gas phase is fastest
in pores greater than 20 nm. The amount of pores smaller
than 6 nm and their total specific surface area do not affect
the gasification rate—see the parameters identified for oak
and rose.

Fig. 7 A comparison of the

pore distribution of pyrolysis
residue
80
70
60
50
/% 40
30
20
10 oak
0 rose
<6 beech
6–8
8–10 poplar
10–12
12–16 willow
16–20
/nm 20–80
>80

123
Gasification of selected woody plants
Conclusions
Laboratory results showed that the carbon dioxide gasifi-
cation rate is lower than the water-steam gasification rate.
Therefore, the rate of gasification is favourably affected by
a water-steam addition in the gasification medium. This is
reflected in the technological implementation in the gen-
erator-gas production as well as in the decrease of unburnt
coal in generator by-products. The proved difference in the
rate of gasification between carbon dioxide and water
steam, however, decreases with the growing gasification
temperatures. Nevertheless, also at a temperature of
870 C, the water-steam gasification rate was mostly
higher with all the monitored woody plants with the
exception of the rose, where the situation was the opposite.
It is obvious from the data presented that willow wood
was the most gasifiable, rose wood the least, both by means
of carbon dioxide and water steam. With the other woody
plants, the order changed based on temperature. It can be
generally stated that oak wood is the second least gasifi-
able, whereas the order between the beech and poplar in the
second and third positions considerably varies. In the
selection of the raw material to gasify, it is, therefore,
necessary to bear in mind its origin, because with some
woody plants the gasification may take even half the time.
It has been demonstrated that the increase of the reac-
tivity of solid carbonaceous residues corresponds to the
accessibility of the gasified surfaces for gaseous gasifica-
tion media, i.e. mainly the pore size. The most reactive
woody plants were the willow and poplar, which had the
highest pore representation in the size of 20–80 nm and the
fewest pores of sizes below 6 nm.
Comparison of the data in Tables 3 and 4 and Fig. 7
clearly shows that the pores bigger than 20 nm were the
most important for the gasification process. Other observed
323
pore sizes were equally represented and they do not cause
significant impact.
Another stimulating finding is that the quickest to gasify
was the carbonisation residue of woody plants that had the
smallest carbonaceous residue after heating to 900 C. The
alkalinity index following Sakawa [10] was not applied in
the mutual comparison of the gasification reactivities of the
monitored woody plants.
Acknowledgements Part of the presented investigation was sup-
ported by the TA 01021279 project of the Technology Agency of the
Czech Republic and part was supported by the Research Plan of the
Ministry of Industry and Trade of the Czech Republic of the FT-TA
3/112 project.
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