J Therm Anal Calorim (2013) 111:1811–1815
DOI 10.1007/s10973-012-2552-7
A biomass pyrolysis model for CFD application
Ion V. Ion • Florin Popescu • Gina G. Rolea
CEEC-TAC1 Conference Special Chapter
Ó Akadémiai Kiadó, Budapest, Hungary 2012
Abstract The CFD modeling of biomass combustion or
gasification systems needs a description of the volatiles
composition that is formed during devolatilization and char
oxidation processes. The present model can be used as a
submodel in the CFD modeling of combustion or gasifi-
cation process. This study is a combination of relevant
models and data available in the literature to formulate a
model that predicts the volatiles in terms of a few simple
species. The volatile species considered by this model are
CO, CO2, H2O, H2, light hydrocarbons, and heavy hydro-
carbons. The model predicts the volatiles as a function of
temperature for different biomasses. The model was
applied for pyrolysis of briquettes made from agricultural
residues. The results are in good agreement with data from
literature.
Keywords Volatiles  Modeling  Agricultural residues 
Pyrolysis  Temperature
Introduction
The European Commission adopted in 2005 the EU Bio-
mass Action Plan to bring into focus the necessity that the
states member to develop the biomass resources of the
Europe. The heating and cooling sector depends on dif-
ferent renewable energy, but it is dominated by the bio-
mass use. In fact, the biomass is the largest renewable
energy source and it is foreseen to contribute with two-
I. V. Ion  F. Popescu (&)  G. G. Rolea
Thermal Systems and Environmental Engineering Department,
‘‘Dunărea de Jos’’ University of Galati, 47 Domnească St.,
800008 Galati, Romania
e-mail: florin.popescu@ugal.ro
thirds to the total energy produced from renewable sources
till 2020 [1–3].
In choosing the biomass conversion process in a useful
form of energy, the most important things are the quantity
and type of available biomass, the desired form of energy,
the environment legislation, and the economic constraints.
The biomass gasification is the most efficient technology of
conversion, but due to the higher capital costs of the
installations the combustion remains the most attractive
technology. The biomass combustion represents 90 % from
the global contribution of bioenergy. The agricultural
products and residues represent about 9 % of the global
biomass potential. They are used as heating fuel chiefly in
rural areas.
Despite the large quantities of generated agricultural
residues, the actual level of their usage as fuel is low. One
of the reasons of low usage is given by the reduced
information on fuel feeding, combustion characteristics,
and the pollutant emissions of the agricultural residues.
This information is important for the design and efficient
operation of the combustion systems. Apart from the fossil
fuels, some physical and chemical properties of agricultural
residues complicate their processing and combustion.
The large variation in combustion properties of agri-
cultural residues influences significantly the efficiency and
pollutant emissions of the combustion plants. The com-
bustion in small plants leads to higher emission due to the
incomplete combustion. Therefore, there is an increasing
interest in usage of more efficient boilers, user friendly, and
environmental friendly. To optimize the boiler efficiency
when agricultural residues are used, an important task is to
study deeply the combustion process. The modeling toge-
ther with the experiments represents a less expensive
design of the combustion devices. The modeling helps us to
understand the processes involved in biomass combustion
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1812 I. V. Ion et al.

and may reduce the time for design optimization through balances were used with two additional empirical rela-
researches. tionships, forming a system of six equations to predict the
Models of solid fuel combustion devices, such as fixed yields of six volatile species. The conversion of the fuel
and fluidized beds, tend to be extremely complex and time- particle is treated as a black-box since the complex pro-
consuming. Therefore, simplifications need to be found. For cesses occurring while it undergoes pyrolysis are not
solid biomass combustion modeling, the combustion process considered. Only the final stoichiometry of the pyrolysis
is considered composed by the following steps: the biomass process is predicted using empirical parameters to solve the
drying–pyrolysis (devolatilization), volatiles combustion, composition of volatiles in a relevant number of species.
and combustion of the syngas produced by char gasification. However, the parameters used in [6] were derived from a
The paper presents the results on the devolatilization particular set of experimental data and have a restricted
modeling necessary in the modeling of agricultural resi- range of validity. These simplified particle models are
dues combustion. When the biomass is exposed to high useful because they can be readily used in a comprehensive
temperature, it undergoes thermal decomposition and gets reactor model [7].
converted into volatile gases and char. Molcan et al. [8] also have developed a volatile model
There is a large number of works/papers on modeling of resolving a system of four linear equations, necessary for
paralysis focused mainly on the rate evolution of volatiles the numerical simulation of biomass combustion in a
during pyrolysis following several mechanisms: global 25MWth spreader stoker boiler. Fraction of the volatile
single- and two-step reactions [4, 5]. The model of Thun- gases is calculated by elementary mass balance respecting
man et al. [6] is an example of this type of particular the biomass elementary analysis. The CO and CO2 species
model, where the overall energy and elemental mass from char oxidation are estimated by data from literature.

Table 1 Ultimate analysis of biomass briquettes from agricultural residues

Fuel sample Chemical formula Ultimate analysis/wt% of wet fuel with ash Char/wt%
C H O N Moisture Ash

50 % Sawdust and 50 % cornstalk C6H1.431O0.61 46.1 5.5 33.8 0.4 6.7 3.3 21.67
50 % Sawdust and 50 % straw C6H1.450O0.56 48.0 5.8 36.1 0.5 5.2 4.4 20.30
Sawdust C6H1.416O0.50 50.0 5.9 33.6 1.8 6.0 2.6 25.52
Reeds C6H1.363O0.48 48.8 5.5 31.2 0.7 7.0 7.3 29.00

Fig. 1 Comparison of the 40.0

40.0
model predictions for rice husk
Mass concentration/%

Mass concentration/%

and softwood with data from 30.0 CO 30.0 CO

literature [9, 13]: a Rice husk CO2
CO2
[9], b softwood [9], c rice husk 20.0 H2
20.0 H2
(predicted), d softwood H2O
H2O
(predicted) ME ME
10.0 10.0
Tar Tar

0.0 0.0
500 700 900 1100 500 700 900 1100

Temperature/K Temperature/K
(a) (b)
40 40
Mass percentage/%
Mass percentage/%

30 30

20 20

10 10

0 0
500 600 700 800 900 1000 1100 500 600 700 800 900 1000 1100
Temperature/K Temperature/K
CO CO2 H2 H2O ME Tar CO CO2 H2 H2O ME Tar

(c) (d)

123
A biomass pyrolysis model 1813

40 approach considers the fuel to be composed of three main

35 chemical constituents: carbon (C), hydrogen (H), and
30 oxygen (O) and char. In hot environment, the biomass is
Mass percentage/%

25 converted into gaseous species, bio-oil (tar) and char. The

20
present paper considers the light hydrocarbons (ME) as
15
methane (CH4), heavy hydrocarbons as tar with chemical
formula as C6H6.2O0.2, and char as pure carbon.
10
The pyrolysis decomposition process can be described
5
by the following equation [9]:
0
CO CO2 H2 H2O ME Tar C6 Ha Ob ¼ xchar;ashfree C þ x1 CO þ x2 CO2 þ x3 H2
ð1Þ
700K pred [1] 700K pred (present model) 1064K pred [9] exp [12]
þx4 H2 O þ x5 CH4 þ x6 C6 H6:2 O0:2
Fig. 2 Comparison of the model predictions for softwood with data where C6HaOb is the chemical formula of the dry and ash-
from literature [9, 10, 14]
free biomass, xi is the number of moles of a given species
In the present work, the authors have used a combina- involved in the process, C6H6.2O0.2 is the chemical formula
tion of relevant models and data available in the literature for tar [6, 10].
to formulate a model that predicts the volatiles in terms of a The chemical formula C6HaOb of any dry and ash-free
few species. The volatile species considered are CO, CO2, biomass species is calculated knowing the ultimate analysis
H2O, H2, light hydrocarbons, and heavy hydrocarbons. The as it is given in Table 1, using the following relations [11]:
model predicts the volatiles composition as a function of H  MC O  MC
a¼ b¼
temperature for different solid biomass fuels. C  MH C  MO
where a is the H atoms substitution formula, b is the O atoms
substitution formula, M is the molar weight (kg mol–1), C is
Model description
the mass fraction of carbon, H is the mass fraction of
hydrogen, and O is the mass fraction of oxygen.
In order to model the combustion of agricultural residues
From the elemental balance of Eq. (1), the following
using a CFD code, it is necessary to know the composition
relations result:
of pyrolysis products as a function of temperature. To
model the thermal degradation of biomass, the present C: 6  xchar;ashfree ¼ x1 þ x2 þ x5 þ 6x6 ð2Þ

Fig. 3 Volatile composition for 50 50

biomass: a 50 % sawdust and

Mass percentage/%

40 40
50 % straw, b 50 % sawdust
Mass percentage/%

and 50 % cornstalk, c sawdust, 30 30

d reed
20 20

10 10

0 0
500 600 700 800 900 1000 1100 500 600 700 800 900 1000 1100
Temperature/K Temperature/K
CO CO2 H2 H2O CH4 C6H6.2O0.2 CO CO2 H2 H2O CH4 C6H6.2O0.2

(a) (b)
50 50

40 40
Mass percentage/%

Mass percentage/%

30 30

20 20

10 10

0 0
500 600 700 800 900 1000 1100 500 600 700 800 900 1000 1100
Temperature/K Temperature/K
CO CO2 H2 H2O CH4 C6H6.2O0.2 CO CO2 H2 H2O CH4 C6H6.2O0.2

(c) (d)

123
1814
H: a ¼ 2x3 þ 2x4 þ 4x5 þ 6:2x6 ð3Þ
O: b ¼ x1 þ 2x2 þ x4 þ 0:2x6 ð4Þ
To calculate the six unknown variables x1, x2, x3, x4, x5,
x6, three additional Eqs. (5–7) are used. Following the
paper [9], the mass ratios CO/CO2 and CH4/CO2 have been
obtained as a function of temperature by curve fit to the
experimental data from [12] and the ratio of H2O/CO2 is
considered equal to 1 according to Thunman et al. [6].
The equations obtained experimentally are [9]:
YCO 28x1 7730:3 5018989
¼ ¼ e1:845 þ T  T2 ð5Þ
YCO2 44x2
YH2 O 18x4
¼ ¼1 ð6Þ
YCO2 44x2
YCH4 16x5
¼ ¼ 5  1016  T 5:06 ð7Þ
YCO2 44x2
where Yi is mass fraction.
By solving the equations system formed by the ele-
mental balance equations (2–4) and empirical equations
(5–7), the volatile composition is predicted as function of
temperature. The tar content decreases exponentially with
the temperature as it is reported in [13].
Results and discussion
The volatile model predicts the concentration of volatile
species depending on the temperature for a given biomass
having the chemical formula C6HaOb. It also uses the
content of char in biomass.
We have done both qualitative and quantitative valida-
tions of the proposed model.
The qualitative validation of the model has been done
with the predicted data from [9] (Fig. 1).
It can be observed that for the two biomasses (rice husk
and softwood), the content of tar is over predicted and it
does not become negative as in [9]. Thus, the CO2 and H2O
curves obtained by the proposed model are identical (see
Eq. 6). In paper [9] when the tar variation becomes nega-
tive, then Eq. 6 and the tar concentration are excluded and
the new system of five remainder equations with five
variables is solved.
The CO content increases with temperature but without
having a maximum around the temperature of 1,000 K.
The variations of other components (CO2, H2O, H2, and
light hydrocarbons—ME) are in the same range.
The quantitative validation of the proposed model has
been done by comparing the predicted composition for
softwood (with composition given in [14]) with the
experimental data from [10] and predicted data from [9]
and [14] in Fig. 2. The experimental results from [10] are
123
I. V. Ion et al.
reported without giving the composition of dry wood and
the temperature of pyrolysis.
It can be observed that the predicted values obtained
with different models are in a quite good agreement with
the experimental data.
Figure 3 shows the effect of temperature on volatile
composition for different types of biomass. It can be
observed that the volatiles variations obtained with the
present model respect the same tendency that in the work
of Sharma et al. [9].
For all biomasses, the variation of volatile composition
has a similar trend. The increase of temperature leads to the
significant decrease of tar yield, a slow decrease of carbon
dioxide and moisture yield, and the increase of methane
and carbon monoxide yield. The hydrogen yield is low and
almost constant with temperature.
Conclusions
A model for predicting the simplified volatile composition
and char yields has been presented for the case of slow
pyrolysis of biomass preceding the combustion.
The formulation is based on overall elemental balance
supplemented by the empirical correlations for ratios of
different species. The model has been validated by quan-
titative and qualitative comparing of its predictions with
published experimental data on pyrolysis product compo-
sition for a typical biomass feedstock.
Predictions of the effect of temperature on the pyrolysis
yield of different biomass materials have been carried out.
The present model can be implemented as a submodel in
the modeling of combustion process for using a UDF
function in CFD applications.
Acknowledgements The authors would like to acknowledge the
support provided by the ‘‘Dunărea de Jos’’ University of Galati,
Project SOP HRD SIMBAD 6853, 1.5/S/15—01.10.2008.
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