Sie sind auf Seite 1von 6

10th International Symposium on Process Systems Engineering - PSE2009

Rita Maria de Brito Alves, Claudio Augusto Oller do Nascimento and Evaristo
Chalbaud Biscaia Jr. (Editors)
2009 Elsevier B.V. All rights reserved.
Modeling of omass sification plied to a
mbined sifier- mbustor it: uilibrium
and netic proaches
Bi Ga Ap
Co Ga Co Un Eq
Ki Ap
Rodolfo Rodrigues,
a,b
Argimiro R. Secchi,
a,c
Nilson R. Marclio,
b
Marcelo
Godinho
b

a
GIMSCOP - Group of Integration, Modeling, Simulation, Control, and Optimization of
Processes;
b
LPR - Laboratory of Residues Processing
Department of Chemical Engineering, Federal University of Rio Grande do Sul. Rua
Eng. Luis Englert, s/n - Campus Central. CEP 90040-040. Porto Alegre (RS), Brazil.
E-mail: rodolfo@enq.ufrgs.br, nilson@enq.ufrgs.br, godinho@enq.ufrgs.br
c
COPPE/PEQ/LMSCP - UFRJ, Av. Horcio Macedo, 2030 - Centro de Tecnologia.
CEP 21941-914. Rio de Janeiro (RJ), Brazil. E-mail: arge@peq.coppe.ufrj.br
Abstract
This study proposes an analysis of biomass gasification using two mathematical models:
one equilibrium model and one kinetic model based on the level of details and input
data. After validation with data from literature, the models were applied for analysis of a
combined gasifier-combustor unit for processing of solid wastes (biomass) of footwear
industries. The gas product predicted by the models was indirectly validated with
experimental data. For this, the adiabatic flame temperature estimated from the gas
product was confronted to experimental temperature of the combustor unit, showing the
accuracy of each model. Sensitivity analyses of the models were carried out regarding to
the feed air flow rate. The responses to parametric changes were observed in major
output parameters: low heating value (LHV) of gas product, and cold gas efficiency,
which are important measures to quantify the performance of the system.

Keywords: biomass gasification, combined gasifier-combustor unit, equilibrium model,
kinetic model.
1. Introduction
An alternative destination to solid wastes in general is the thermal treatment
technologies. By this is possible to reduce filled volume and to stabilize dangerous
components. One of these technologies is the gasification which generates a useful gas
fraction under moderate conditions. According to Higman and van der Burgt [1], the
gasification is a thermochemical process of conversion of any carbonaceous fuel to
gaseous product with a useable heating value. As a result it can be to use like fuel gas or
syngas to after using.
This study proposes an analysis of biomass gasification through mathematical
modeling. However it is well-known that practical data (geometric measures,
identification of intermediary compounds, etc.) are oftentimes available on high or low
detailed levels to satisfactory process simulation. In this sense, two mathematical
models are presented: one equilibrium model and one kinetic model based on the level
of details and input data. After validation with data from literature, the models were
applied for analysis of a pilot combined gasifier-combustor unit for processing of solid
657
wastes (biomass) of footwear industries. As a renewable resource, the processing of that
abundant biomass is enclosed inside the natural carbon cycle unlike fossil-derived
resources such as oil and coal.
2. Modeling of the process
Biomass gasification models are predominantly separated in two groups: equilibrium
approach and kinetic approach [2]. Kinetic models take into account the chemical
kinetics of the main reactions and the transfer phenomena among the phases, estimating
the composition of each species on any point of space and time of a system. These
models are specific in general for each process, providing important considerations
related to chemical mechanisms and ways to increase reaction rates and process
performance. On the other hand, equilibrium models provide the greatest possible
conversion of each species regardless the system size and the time needed to reach
equilibrium. These models do not require details of system geometry neither estimate
the necessary time to reach that equilibrium.
2.1. Equilibrium model
Among the equilibrium modeling, two approaches can be cited: stoichiometric and non-
stoichiometric [2]. Although equivalent in essence, the stoichiometric approach applies
the equilibrium constants from related chemical reactions [3-4], while the non-
stoichiometric approach minimizes the Gibbs free energy subject to mass balance and
non-negative constraints [2, 5].
A stoichiometric model was developed in this work, assuming as major hypotheses: all
carbon of biomass is gasified, making char formation negligible; the system is adiabatic
and isobaric; and all oxygen is consumed on the process. In Table 1, the main equations
of the equilibrium model are depicted.

Table 1. Main equations of the equilibrium model.
Overall mass balance:
F


n
_ n
k,
x
n
= F
out
_ n
k,
x
out
F
n
_ x

(I
n
, P)
n
=
F
out
_ x

(I
out
, P)
out

(2)

]
= [ (P

P
o
/ )
v
i,]

-RIlnK
]
= A0
]
(4)
where Au
j
o
is the variation of standard Gibbs fr
of
(1)
where n
k,i
is the number of atoms k of a molecule i,
and x
i
is the molar fraction of a component i.
Overall energy balance:
Equilibrium constant of reaction j:
K (3)
which is related to temperature by:
o
ee
energy reaction j as function of temperature.

this case, two equilibrium reactions are considered: water-gas shift reaction (5) and
O
2
+ H
2
(5)
B energy balance is possible to estimate the final temperature
ures of the kinetic model are the chemical kinetic approach and
In
metanation (6):
CO + H
2
O C
C + 2H
2
CH
4
(6)
y means of the for a
specific kind of biomass and fraction of air stream. As a result, the flue gas composition
is estimated as function of temperature.
2.2. Kinetic model
The important feat
transfer phenomena relations. In this sense, in literature, only few models were found
for concurrent biomass gasification [6-7]. The proposed model is based on mass and
658 R. Rodrigues et al.
energy balances for solid- and gas-phases, described by a dynamic system and one-
dimensional equations, and involving the following components: B (biomass), M
(moisture), and C (char), for solid-phase and T (tar), O
2
, CO
2
, H
2
, H
2
O (steam), CH
4
,
CO, and N
2
, for gas-phase. The following processes are considered in the model:
moisture evaporation (m), biomass pyrolysis (p
1
), thermal cracking of the tars (p
2
),
combustion of the volatiles (c
1
-c
4
), and char combustion and gasification (c
5
, g
1
-g
3
).
The main model assumptions are: single size of the particles; no momentum transfer;
able 2. Main equations of the kinetic model.
t
constant bed porosity; heat and mass transfer across the bed resulting from macroscopic
(convection) and molecular (diffusion and conduction) exchanges; extra-particle mass
transfer resistance; and solid- and gas-phase heat transfer with the reactor walls. In
Table 2, the main equations of the kinetic model are depicted.

T
Mass balance for solid-phase:

p
i
+
(p
i
u
s
)
z
= _ v R
,] ] ]
(7)
where i = B, M, C; j = m,
1
.
Overall mass balance for solid-phase:
p
p
s
u
s
z
= _ _ v
,]
R
] ]
(8)
where i = B, M, C; j = , p
1
, c
5
, g
1
-g
3
.
Mass balance for gas-phase:
m
e
t
p
i
+
z
(p
i
u
g
)
=
z

p
g
z
x
i
+
Hw

_ v
,]
R
] ]
+


(9)
where i = T, O
2
, CO
2
, H
2
, H
2
O, CH
4
, CO; j = c
1
-c
g
1
-g
3
, wg, and
i
is the rate of species i generated in
solid-phase.
Overall mass balance for gas-phase:
5
,

e
p
g
t
+
(p
g
u
g
)
z
= _ _ v
,]
Hw

R
] ]
+
(10)
(1 -v
C,p1
)R
p1
+_ v
,p2
R
p2


where i = T, O
2
, CO
2
, H
2
, H
2
O, CH
4
, CO, N
2
and
j =
En

t
m, c
1
-c
5
, g
1
-g
3
, wg.
ergy balance for solid-phase:
(p
s
H
s
)

=

z
[z
-
1
s
s
z
+
(u
s
p
s
H
s
)
z
-
_ R
]
AE
] ]
-
sg
-
sw

(11)
where j = c
5
, g
1
-g
3
, p
1
; Q
sg
is the heat excha
between solid- and gas-phase; and Q
sw
is the heat
exchange between solid-phase and walls.
En

nge
ergy balance for gas-phase:
e
(p
g
H
g
)
t
=

z
[z
-
1
g
g
z
+
(u
g
p
g
H
g
)
z
-
_ R AE + -
] ] ] sg gw
(12)
where j = c
1
-c
4
, wg, p
2
; and Q
gw
is the heat exchange
between gas-phase and walls.
Pressure drop (modified Darcy law):

K

P
z
= u
s
-u
g
(13)
where K is the permeability to gas flow.

The coefficients of heat and mass transfer e ca ulated according to Hobbs, Radulovic
and Smoot [8]. The gas thermal conductiv an rnomo,
Aerts and Ragland [9]. The specific heats (a vity are
nsidered constants.
s made in two steps: (1) comparing equilibrium constants of
data from Sharma [4]; (2) comparing
d one
air pollution control system. The gasifier is a downdraft type so that feedstock is
ar
ity
lc
d viscosity are described as in Pu
vailable at 1000 K) and diffusi
co
2.3. Implementation and validation of the models
The models were implemented in the equation-based process simulator EMSO
(Environment for Modeling, Simulation and Optimization [10]). The validation of the
equilibrium model wa
considered reactions with tabulated and predicted
composition of gaseous product with experimental and predicted data from Melgar et al.
[3]. For the kinetic model, it was validated by predictions of Di Blasi's [6] model.
3. Application to a combined gasifier-combustor unit
3.1. Description of the pilot unit
The pilot unit (Fig. 1) is basically formed by one combined gasifier-combustor an
659
Modeling of Biomass Gasification Applied to a Combined Gasifier-Combustor Unit:
Equilibrium and Kinetic Approaches
concurrent to gas flow. There are two
incoming air points along ga
Figure 1. Combined gasifier-combustor unit.
feed
system
gasifier
combustor
grate
ash
extractor
air box (1
st
air
injection)
burner (2
nd
air
injection)
T13
T12
T11
T1
T2
T5
to air pollution
control system
sifier height.
d in the
observed in output
LHV) of the energetic gas product (CO, H
2
, and CH
4
)
v d, from this fraction, the
Other three air injections are fe
combustor to oxidize the fuel gas coming
from the gasifier.
The input solid wastes are leather strips
with ultimate analysis of 49.31%C,
8.52%H, 24.7%O, 12.42%N, and
1.83%S, and a HHV of 18,448 kJ/kg
(d.b.). And their proximate analysis
afford 77.3% volatile matter, 5.8% ash,
and 16.9% carbon fixed (as received
with 14.1% moisture content) [11]. A
specific parameter related to this waste is
the mass relation of O
2
to complete
oxidation of biomass: 1.57 kg
O2
/kg
B
. The
gasifier is a reactor of 1.465 m height
and 0.611 m equivalent diameter, where
the bed density is 400 kg/m
3
and the void
fraction is 0.5. A typical operation
involves 60 kg/h feedstock that is gasified by two air injection at 300 K of 102.4 Nm
3
/h
and 55.7 Nm
3
/h, respectively. The acquisition of experimental data is made by 5
thermocouples (T1, T2, T11, T12, and T13) along the gasifier and 1 thermocouple (T5)
in the final of the combustion chamber.
3.2. Simulation of the pilot unit
Sensitivity analyses of the process were carried out regarding to the feed air flow rate as
an operating parameter. The responses to parametric changes were
parameters: low heating value (
and cold gas efficiency (
cg
), according to the equilibrium model. These output
parameters are important to quantify the performance of the process. In this study, the
feed air flow rate is related to the feedstock by a parameter called equivalence ratio (),
which indicates the oxygen used relative to that required for complete combustion.
The predictions of the equilibrium model for typical operating conditions from
measured and predicted data by Godinho [11] have shown good accuracy. Divergences
could be justified by assuming an adiabatic system. Figure 2a shows the molar fractions
of gaseous products, beyond adiabatic reaction temperature, related to the feeding air
amount (equivalence ratio). Taking into account only components of energetic gaseous
product, it is possible to observe that CH
4
increases with low equivalence ratios ( <0.5)
and CO and H
2
is maximum within 0.3 < < 0.7. The equilibrium temperature is
minimum (T = 300 K, ambient temperature) at = 0.175 and maximum (T = 1680 K) at
= 1, where CO
2
and H
2
O (inconvenient to the process) are maximum and CO, CH
4
,
and H
2
are negligible. Cold gas efficiency (
cg
) and low heating value (LHV) to flue
gas, related to conditions of Fig. 2a are shown in Fig. 2b. The maximum efficiency
(85.5%) is reached at = 0.45. Therefore the optimal range for gasification of leather
strips is 0.34 < < 0.53 (5% maximum efficiency range).
The predicted gas composition at average conditions was also compared to experimental
data, indirectly. It is possible to relate the measured temperatures in the reduction zone
of the gasifier (T11) and the combustion chamber (T5) estimating the gaseous product
at measured a erage temperature (906 K, = 0.467) an
660 R. Rodrigues et al.
adiabatic flame temperature at a range of feeding O
2
. At the last step of combustion,
there is an average amount of 11% O
2
(v/v, d.b.) in excess [11] which corresponds to an
adiabatic flame temperature of 1174 K. This value is close to the average value
measured in T5: 1133 K.

(a) (b)
Figure 2. Properties to 0.175 <
0.2 0.3 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
2000
4000
< the equilibrium model: (a) Gaseous product and adiabatic
reaction temperature. (b) Cold gas efficiency and low heating value to energetic gaseous product.
Likewise, the same conditions of the process were simulated using the kinetic model a
e reactor
(a) (b)
Figure 3. Results of kinetic model: (a) Temperature profiles of solid- and gas-phase, and
measured data. (b) Mass flow rate of solid- and gas-
1 by
t
steady-state. In this case, th was divided in three secti defined by the top-
gasifier (0 m), first air injection (0.655 m), second air injection (1.315 m), and bottom-
gasifier (1.465 m). The results present here were applied to the first two sections. In Fig.
ons
3a, the predicted profiles have qualitative agreement with respect to experimental data.
phase species along gasifier before second air
injection.

The hot
H
2
O close to the air injection are ob fter that point, all small amounts of
olatile materials are quickly consumed and, as result, there is an excess of O
2
to
inflection point in 0.655 m means the cold feeding air mixed to the preceding
gas stream from first section. In Fig. 3b, the fast consumption of O
2
and formation of
served. A
v
oxidize. For solid-phase (Fig. 3b), despite the fast conversion of biomass, small
amounts of char are created. The inconsistencies associated to low release of volatiles
and low formation of char are justified by the quality of kinetic parameters for pyrolysis
reactions (p
1
-p
2
) adapted from literature data to leather wastes [12-13]. The uncertainties
in the heat transfer coefficients also have significant role in the results. Another
important factor to take into account, not observed in literature [6-7], is the reflux of air
in two directions for one-dimensional representation by injecting air in intermediate
0.4 0.5 0.6 0.7 0.8 0.9 1
0
0.1
0.2
0.3
0.4
x

(
k
m
o
l
/
k
m
o
l
)
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
300
675
1050
1425
1800
6000
8000
(kmol/kmol)
T

(
K
)
(kmol/kmol)
L
H
V

(
k
J
/
k
g
)
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
0.25
0.5
0.75
1
Teq
cg

c
g

(
k
J
/
k
J
)
0 0.25 0.5 0.75 1 1.25 1.5 1.5
300
500
700
900
0 0.25 0.5 0.75 1
1100
1300
z(m
T
(
K
)

)

1.25 1.5
0
15
30
45
60 60
z(m)
F
(
k
g
/
h
)


H2O
CO2
H2
CH4
CO
LHV
T12
T1
M
CO
CO2
O2
O2
T
C
solid
gas
T11
T2
B
H2O
T13
661
Modeling of Biomass Gasification Applied to a Combined Gasifier-Combustor Unit:
Equilibrium and Kinetic Approaches
dict the steady-
the gasifier. With this approach it was possible to identify an optimum
n within 0.34 < < 0.53 and to confront measured temperature from
Luftech Solues Ambientais and
eciclagem de Resduos.
. Ergdenler, 2001, Equilibrium modeling
of gasification: a free energy minimization approach and its application to a circulating
coal gasifier, Fuel, 80, 2, 195-207.
g
ring
and
and
ion
heights. In this case, the model considers that first feeding air (102.4 Nm
3
/h) is
portioned between the top (25%) and the first air injection point (75%).
4. Conclusion
The proposed models, equilibrium and kinetic, presented compatible results compared
with literature data. The equilibrium model reached good accuracy to pre
state behavior of
range of operatio
the combustor with predicted data from the gasifier. Besides, due to poor quality of
kinetic parameters and heat transfer coefficients, which are not full available for the
specific case, the kinetic model could only predict qualitative steady-state behavior of
the gasifier. Also, the representation of a three-dimensional system into one-
dimensional model has limited prediction capability.
Acknowledgement
The authors would like to acknowledge the Brazilian agencies of research support:
FAPERGS, CNPq, and FINEP; and the companies:
Preservar Tratamento e R
References
1. C. Higman and M. van der Burgt, 2003, Gasification, Gulf Professional Publishing, Oxford.
2. X. Li, J. R. Grace, A. P. Watkinson, C. J. Lim, and A
fluidized bed
3. A. Melgar, J. F. Prez, H. Laget, and A. Horillo, 2007, Thermochemical equilibrium modellin
of a gasifying process, Energy Conversion and Management, 48, 1, 59-67.
4. A. K. Sharma, 2008, Equilibrium modeling of global reduction reactions for a downdraft
(biomass) gasifier, Energy Conversion and Management, 49, 4, 832-842.
5. M. Baratieri, P. Baggio, L. Fiori, and M. Grigiante, 2008, Biomass as an energy source:
thermodynamic constraints on the performance of the conversion process, Bioresource
Technology, 99, 15, 7063-7073.
6. C. Di Blasi, 2000, Dynamic behaviour of stratified downdraft gasifiers, Chemical Enginee
Science, 55, 15, 2931-2944.
7. F. V. Tinaut, A. Melgar, J. F. Prez, and A. Horillo, 2008, Effect of biomass particle size
air superficial velocity on the gasification process in a downdraft fixed bed gasifier. An
experimental and modelling study, Fuel Processing Technology, 89, 11, 1076-1089.
8. M. L. Hobbs, P. T. Radulovic, and L. D. Smoot, 1992, Modeling fixed-bed coal gasifiers,
AIChE Journal, 38, 5, 681-702.
9. D. Purnomo, D. J. Aerts, and K. W. Ragland, 1990, Pressurized downdraft combustion of
woodchips, 23th Symposium (International) on Combustion, 1025-1032.
10. R. P. Soares and A. R. Secchi, 2003, EMSO: a new environment for modelling, simulation
optimization, ESCAPE 13, Elsevier Science Publishers, 947-952.
11. M. Godinho, N. R. Marclio, A. C. F. Vilela, L. Masotti, and C. B. Martins, 2007, Gasificat
and combustion of the footwear leather wastes, Journal of the American Leather Chemists
Association, 102, 6, 182-190.
12. J. A. Caballero, R. Font, and M. M. Esperanza, 1998, Kinetics of the thermal decomposition of
tannery waste, Journal of Analytical and Applied Pyrolysis, 47, 2, 165-181.
13. R. Font, J. A. Caballero, M. M. Esperanza, and A. Fullana, 1999, Pyrolytic products from
tannery wastes, Journal of Analytical and Applied Pyrolysis, 49, 1-2, 243-256.
662 R. Rodrigues et al.