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Article history:
Received 14 August 2010
Accepted 29 November 2010
Available online 10 December 2010
Keywords:
Biomass particle
Thermal degradation
Pyrolysis model
Heat of reaction
Kinetic constants
a b s t r a c t
An accurate formulation of energy conservation to model pyrolysis of a biomass particle needs to account
for variations in the heat of reaction with temperature, usually neglected in most past studies. It is shown
that by including this effect in a pyrolysis model with three parallel reactions yielding char, gas and tar, a
wide range of experimental data can be accurately predicted. In particular, through comprehensive comparisons of the simulation results with various measurements, a consistent and single value of 25 kJ/kg
is obtained for enthalpy of pyrolysis, which represents a lumped heat of volatiles and char formation at
a reference temperature. It is found that the kinetic parameters of Chan et al. [W.C. Chan, M. Kelbon, B.B.
Krieger, Fuel 64 (1985) 15051513] and Thurner and Mann [F. Thurner, U. Mann, Ind. Eng. Chem. Process
Des. Dev. 20 (1981) 482488] provide reasonable agreement between the model predictions and experiments compared to other reported kinetic constants. These comparisons also indicate that inclusion of tar
cracking reactions to yield additional light gases does not give a better prediction of the process parameters. The presented thermo-kinetic model is capable of successfully predicting various experimental
observations such as the internal temperature peak reported in some past studies. It is shown that the
sensible heat released due to the conversion of virgin biomass to the reaction products is responsible
for this phenomenon. Simulation results reveal that a temperature peak at an internal location of the
particle may occur when the corresponding local temperature reaches the particle surface temperature
while the local biomass conversion is not nalized yet.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Increasing CO2 emissions and uncertainties related to the ultimate availability of fossil fuels are major concerns which push
industry and R&D sectors to seek solutions and new concepts to
overcome these issues. Fossil fuel-based power plants, in particular coal red power plants, contribute signicantly to greenhouse
gas emissions. A cost-effective CO2 reduction method is co-ring
of a high fraction of biomass in coal red power plants. Because of
the existing infrastructure of coal red power stations, the extra
investment costs for co-ring biomass takes advantage of the high
efciencies obtainable in large coal red power plants. Therefore, it
is necessary to increase our understanding and predictive capabilities of biomass combustion with respect to emissions, fuel ignition,
burnout and ash quality.
Combustion of a biomass particle is quite complex as it
undergoes various physical and chemical successive processes
including heating up, drying (in case of a wet particle), devolatilization/pyrolysis and char burnout. However, depending on the
Corresponding author.
E-mail address: y.haseli@tue.nl (Y. Haseli).
0165-2370/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2010.11.006
heating conditions, particle size and composition, moisture content, etc., some of the above mentioned processes may occur
simultaneously. As concluded by Williams et al. [1], accurate
modeling of biomass combustion with quantitative reliability still
remains a challenge.
The thermal characteristics of the pyrolysis process as one of
the unavoidable steps during thermal decomposition of a biomass
particle need to be carefully investigated at combustion conditions;
even though this phenomenon has been previously studied theoretically and experimentally by many researchers, e.g. Di Blasi [2,3],
Gronli and Melaaen [4], Bharadwaj et al. [5] and Larfeldt et al. [6].
During biomass pyrolysis, several physical and chemical processes
take place including virgin biomass heating up, moisture evaporation and transportation, kinetics involving the decomposition of
biomass to tar, char and light gases, heat and mass transfer, pressure build-up within the porous medium of the solid, convective
and diffusive gas phase ow, variation of thermo-physical properties with temperature and composition, and change in particle size,
i.e. shrinkage.
The detailed models available in the literature for biomass
pyrolysis are based on coupled time-dependent conservation equations including kinetics of the biomass decomposition. In fact, the
kinetic model directly inuences the conservation equations. A lit-
Nomenclature
A
cP
E
e
h
hf
h
K
k
k*
MW
n
P
Q
qx
R
Rg
r
T
t
u
YC
Greek letters
porosity
density, g/cm3
hBg
enthalpy of B G and B T reactions, kJ/kg
hBC enthalpy of B C reaction, kJ/kg
hTg
enthalpy of tar cracking reaction, kJ/kg
viscosity, kg/m s
StephanBoltzmann constant
Subscripts
0
initial condition
surrounding condition
B
biomass
C
char
G
light gases
g
gas phase (tar + light gases)
T
tar
141
142
Table 1
Kinetic data of Chan et al. [14].
Reaction
Test Case
Reaction
Bio Gas
Bio Tar
Bio Char
1.30 10
2.00 108
1.08 107
140
133
121
Frequency factor
(1/s)
Activation energy
(kJ/mole)
Pyroprobe 100
Bio Gas
Bio Tar
Bio Char
Bio Gas
Bio Tar
Bio Char
1.52 107
5.85 106
2.98 103
6.80 108
8.23 108
2.91 102
139.3
119
73.4
155.6
148.5
61.4
Bio Gas
Bio Tar
Bio Char
4.38 109
1.08 1010
3.27 106
152.7
148.0
111.7
Table 3
Kinetic data of Thurner and Mann [27].
Di Blasi [10] examined data of Chan et al. [14], Thurner and Mann
[27], and (the rst set of) Font et al. [28]. A good quantitative agreement was obtained between the experimental data of Lee et al.
[29] and the predicted temperature proles along the degrading
biomass particle using kinetic parameters of Thurner and Mann
[27]. However, the author believed that such an agreement was
reached mainly due to the properties of char and biomass used in
the numerical simulation, which were those measured in experiments of Lee et al. Thus, no nal conclusion was made in Di Blasis
study concerning the importance of thermo-kinetic data for quantitative predictions.
We compared the rates constants of three parallel reactions
predicted using the kinetic constants of Chan et al. [14], Di
Blasi and Branca [26], Thurner and Mann [27], and Font et al.
[28] as functions of temperature in the range of 400900 K. The
results of these observations can be classied in three temperature ranges; 400 < T < 550 K, 550 < T < 700 K, and 700 < T < 900 K, as
analysed below.
400 < T < 550 K: The rate constant of light gases calculated by
Thurner and Manns data is higher than those obtained from other
three sets. The biomass decomposition rate to produce tar is almost
the same in all cases. For the char yield, the data of Font et al. gives
higher rates compared to the other cases.
550 < T < 700 K: Di Blasi and Brancas data overestimate the production rates of light gases compared to the other data, whereas the
other three sets of kinetic constants give almost the same results.
Again, the rate of tar production computed by Di Blasi and Brancas
data are higher than those predicted by data of the other three
groups. All data sets are expected to give approximately the same
results for rate constant of biomass decomposition to char.
700 < T < 900 K: Di Blasi and Brancas data predicts faster formation of light gases compared to other three data sets. The prediction
using the Chan et al. and Font et al. data are almost in the same
range. Again, rate constants for tar production computed by Di Blasi
and Brancas data are higher than those predicted by data of other
three groups. Computed reaction rate constants of char formation
using Chan et al. and Di Blasi and Brancas data are in the same
range and higher than those computed by other two groups which
produce compatible results.
Given that several factors such as experimental set up,
experiment conditions (high heat ux, low heat ux), biomass
composition may contribute to the reasons of these discrepancies
between various kinetic data, the decision on which set of kinetic
constants must be used in a pyrolysis model, depends largely
upon how well the thermo-kinetic model will predict experimental
observations. The accuracy of the pyrolysis model using the kinetic
parameters suggested by Chan et al., Di Blasi and Branca, Thurner
and Mann, and Font et al. will be examined in Section 4.
2.2. Tar cracking reactions
Reaction
Bio Gas
Bio Tar
Bio Char
1.44 104
4.13 106
7.38 105
88.6
112.7
106.5
Activation energy
(kJ/mol)
Temperature range
(C)
Reference
107.5
93.3
72.8
87.5
460600
500800
430900
>600
[30]
[31]
[32]
[33]
143
Table 6
Values of heat of pyrolysis reported in various studies.
Enthalpy of pyrolysis (kJ/kg)
Method
418
150
64
255
20
200
110
274
353
610
1090 to 1720 (prependicular heating)
105 to 395 (parallel heating)
5382000YC **
*
**
Converion value
Final char yeild
Remarks
X* < 0.95
X > 0.95
Pine wood
Oak wood
X < 0.60
X > 0.60
Low heat ux
High heat ux
High heat ux
Cellulose
Source
Chan et al. [14]
Gronli [35]
Park [36]
Koufopanos et al. [15]
Havens et al. [37]
Bilbao et al. [38]
Lee et al. [29]
144
h i
1 n
1
(r ug h g ) = n
+ n
r r
r r
n T
r k
i = B, C, g
(6)
ki = Ai exp
Ei
Rg T
i = 1, 2, 3, 4
(1)
where h is the total enthalpy, and k* is the effective thermal conductivity which accounts for thermal conductivity of the biomass,
char, gaseous byproducts as well as radiation heat transfer inside
the pores (using the Rossland diffusion approximation for a thick
medium). Some mathematical manipulations are required in order
to represent the energy equation in terms of temperature as
described in Appendix A, so the nal form of Eq. (6) reads
(B cPB + C cPC + g cPg )
1
T
T
+ ug cPg
= n
r r
t
r
where
r n k
T
r
Q = B (k1 + k2 )[hBg +
T k4 [hT G +
+ Q
(cB cg )dT ] + B k3 [hBC +
(cB cC )dT ]+
(8)
(cT cG )dT ]
hP = (1 YC )[hBg +
B
= (k1 + k2 + k3 )B
t
(2)
hS = hT G +
C
= k3 B
t
(3)
T
1 n
+ n
(r T u) = k2 B k4 T
r r
t
(4)
g
1 n
+ n
(r g u) = (k1 + k2 )B
r r
t
(5)
(9)
where it is assumed that the heat of all three primary reactions are
identical and constant (hP ), and the heat of secondary reaction is
represented by hS .
By comparing Eq. (8) with Eq. (9), we nd
Mass conservation equations of the tar (T) and total gas phase
(g) obey
(7)
(cB cC )dT ]
(10)
(cT cG )dT
(11)
In Eq. (10), YC denotes the fraction of char in the pyrolysis products. Hence, in these studies the possibility of evaluating the heat
of pyrolysis at different temperatures and as a function of products
yields is taken away. The main issue with the inaccurate formulation of the source term, Eq. (9), in the energy equation is that an
endothermic heat is usually assumed for all three primary reactions as in many past studies, e.g. 150 kJ/kg [4], 418 kJ/kg [14],
and 64 kJ/kg [15]. These values have been obtained by tting the
predictions (usually mass loss or temperature histories) with the
experiments in each individual study through employing Eq. (9)
Value/correlation
Thermal
conductivity
(W/cm K)
Porosity
Pore diameter (cm)
Permeability
(cm2 )
kg = 0.00026
kc = 0.001 (grain)
kc = 0.007 (radial)
= 1 (1 0 )(B + C )/B0
0 : biomass dependent
d = (B / B0 )dB + (1 B /B0 )dC
dB = 5 103
dC = 102
K = (B/ B0 )KB + (1 B/ B0 )KC
KB = 5 1012
KC = 109
g = 3 105
the terms associated with various specic heats, i.e. (ci cj )dT, as
appeared in Eq. (8)? This term represents the amount of sensible
heat released when species i decomposes to species j at a temperature different from the reference one. Alike any chemical reaction
in which a certain amount of energy is released/consumed at a
given temperature, it is possible to estimate the amount of energy
(enthalpy of reaction) at another temperature by simply algebraic
summation of the enthalpy of reaction at the reference temperature, and the enthalpy that is equivalent to the difference in the
sensible heats of the products and the reactants.
As a conclusion from this discussion, it is possible that the
enthalpy of pyrolysis may become exothermic at some stages of
the pyrolysis depending on the process conditions, as also conrmed in some studies. In such cases, a pyrolysis model that uses Eq.
(9) with constant endothermic heat for the primary reactions will
fail to accurately predict the temperature; and as a consequence
the chemistry of the process will be inuenced. On the contrary, a
model which employs Eq. (8) does not suffer from this issue, since
it has a potential to capture exothermicity of the pyrolysis heat by
accounting for the sensible heat released due to the conversion of
145
K p
r
(12)
g Rg T
MWg
(13)
B = B0
C = 0
T = 0
(14)
g = inert
T = T0
r = 0
T
=0
r
g
=0
T = 0
r
r = R k r =
(15)
4
h(T T ) + e(T
T 4)
or
4)
qx h(T T ) e(T 4 T
146
Table 8
Comparison of the predicted and measured biomass conversion and char yield, with experimental data taken from Gronli and Melaaen [4] (T&M: Thurnner and Mann; C:
Chan et al.; D&B: Di Blasi and Branca; F: Font et al.).
Duration
Kinetic data
5 min
10 min
5 min
10 min
5 min
10 min
5 min
10 min
T&M
Measured
C
D&B
F
25.7
45.5
25.7
45.5
25.7
45.5
25.7
45.5
1.63
3.61
1.63
3.61
1.63
3.61
1.63
3.61
Predicted
%
Measured
Predicted
%
25.1
41.7
24.3
39.9
25.6
41.8
26
44.7
2.3
8.4
5.4
12.3
0.4
8.1
1.2
1.8
30.4
58.8
30.4
58.8
30.4
58.8
30.4
58.8
33.4
56
29.5
50.4
19
35.3
62.7
120.5
9.9
4.8
3.0
14.3
37.5
40.0
106.3
104.9
the measured and the predicted proles was observed, given that
variety of heat of primary reactions was tested.
As mentioned previously, mere validation against heat transfer
parameters is not sufcient since the process also involves kinetics
and mass transport of various species. The biomass conversion fraction and char yield were also calculated using different kinetic data.
In Table 8, the predicted and measured values of these parameters
are compared for 5 min and 10 min as the duration of pyrolysis. The conversion of biomass is well-predicted using all kinetic
data sets at 5 min heating duration. The converted biomass is still
reasonably predicted for the 10 min heating condition with most
under-prediction attributed to the data of Chan et al. Nevertheless,
looking at the predicted char yields, it is seen that the predictions
using the data of Thurner and Mann and the data of Chan et al. are
much better than those obtained using the data of Font et al. and
the data of Di Blasi and Branca. Kinetic constants of Font et al. give a
signicant over-prediction of the char yields to the extent of 106%.
On the other hand, data of Di Blasi and Branca leads to a notable
under-prediction of char yields to the extent of 40%.
Figs. 2 and 3 depict typical simulated time and space evolution of various parameters related to the experimental condition
of Gronli and Melaaen [4]. As the particle with initial temperature
of 300 K is exposed to a high heating ux, the surface temperature begins to rise while some heat is dissipated from the surface
to the surrounding due to radiation and convection heat transfer
mechanisms. The heat received by the surface is transfered into
the particle through conduction heat transfer. As the temperature
of the particle increases, the primary reactions are activated so that
the virgin biomass begins to slightly decompose into three main
groups of byproducts at low temperatures according to the kinetic
model employed. The rates of conversion become higher as the
temperature increases. As the gaseous byproducts are generated by
continuous decomposition of biomass, internal non-uniform pressure slightly greater than atmospheric pressure is built up. This
causes a ow of volatiles through the pores of the particle mainly
towards the surface of the particle where they escape; but there
also exists a ow of gaseous species in the opposite direction which
increases the pressure at the center of the particle. During the initial stages of the process, the pressure peak takes place near the
surface; however, as the process continues the location of the maximum pressure is shifted to the internal positions. This is attributed
to the higher rate of volatiles generated compared to their local
velocity. The ux of gaseous ow is dependent on the local permeability so that the volatiles mass ux is higher in the charred part
of the particle than in the virgin part since the permeability of char
is higher than that of biomass.
As long as decomposition of the particle surface has not been
nalized, the particle can be divided into two regions: a partial char
region where still there is some biomass to decompose, and a virgin
biomass region. In this stage of the process, maximum formation
of volatiles (including tar) and char takes place at the surface. Soon
after all virgin material at the surface has converted to byproducts
147
Fig. 1. Comparison of predicted (solid lines) and measured (areas between broken lines) temperature proles at ve axial positions using kinetic parameters of (a) Thurner
and Mann [27], (b) Di Blasi and Branca [26], (c) Chan et al. [14], (d) Font et al. [28]. Experimental data are taken from Gronli and Melaaen [4].
a thin layer of char is formed at the surface. As the process of degradation proceeds, the thickness of the charred region increases and
its front moves towards the particle center. By increasing the thickness of the char layer, the location of maximum tar yields is shifted
to the inside of the particle and its magnitude increases. In other
words, the local density of tar increases continuously along the axis
of the particle up to a point where formation of tar stops. Beyond
this position, the density of tar decreases due to the ow of volatiles
towards the surface of the particle.
4.2. Comparison with data of Koufopanos et al.
An isothermal mass-change determination technique was
employed in the work of Koufopanos et al. [15] to measure the
pyrolysis rate of dried wood cylinders initially at room temperature
at reactor temperatures in the range of 573873 K. Temperature
variations at two positions inside the particles were also measured during the pyrolysis process. An interesting observation in
these experiments was that the temperature inside the particle
exceeded the reactor temperature, and a peak was observed; with
a higher magnitude at a lower reactor temperature. To capture this
phenomenon, Koufopanos et al. [15] proposed that certain stages
of the conversion take place endothermically, but the rest of the
process proceeds exothermically. Through tting the model predictions with the experiments, they found an endothermic heat of
255 kJ/kg (up to a conversion of 95%), as well as an exothermic heat
of 20 kJ/kg (for the remaining stages of the particle conversion).
Saduhkhan et al. [17] were also able to model the internal temperature peaks observed in the experiments of Koufopanos et al.
148
Fig. 2. Time and space evolution of temperature, volatiles mass ux, internal pressure, biomass density, tar density and char density. Simulated time: 10 min; different lines
correspond to different times; external heat ux: 80 kW/m2 ; horizontal axis: half thickness of particle (3 cm); kinetic data: Thurner and Mann.
Imagine the moment during the pyrolysis process that the center temperature reaches the surface temperature while thermal
degradation of the biomass at the center of the particle has not
yet been nalized. Hence, there is no heat/energy transfer to the
center due to conduction. At this time, the center of the temperature is at some enthalpy level. Since the center temperature is
high enough to cause decomposition of the remaining biomass to
char and volatiles, there is a possibility of a local temperature rise
because of the reduction of the local heat capacity in order to satisfy
the local conservation of energy. In fact, this may occur when the
rate of particle decomposition is higher than the rate of heat transfer. The competition between these two processes continues until
the heat transfer rate becomes dominant and therefore the center
149
Fig. 3. Time and space evolution of temperature, volatiles mass ux, internal pressure, biomass density, tar density and char density. Simulated time: 1 min; different lines
correspond to different times; applied external heat ux: 80 kW/m2 ; horizontal axis: 0.5 cm inside the particle; kinetic data: Thurner and Mann.
150
Thurner and Mann give the best agreement between the experiments and the predictions. Using their data, the effects of the heat
released due to the conversion of biomass to products which are
represented in terms of differences between the specic heats of
virgin material and those of char and volatiles in Eq. (8) is demonstrated through generating the center temperature and mass loss
proles without accounting for this term, at various heats of reactions. The results are depicted in Fig. 7 for a reactor temperature of
623 K. Evident from this gure is that by neglecting the amount
of heat released due to change of nature of the virgin wood to
other materials, and by assuming an endothermic heat for the reactions involved, the temperature peak observed in the experiments
will not be predicted. However, this phenomenon can be captured
by feeding an exothermic heat of reactions into the model. Moreover, the mass loss is remarkably under-predicted should we only
consider an endothermic heat for these reactions.
The phenomena of center temperature peak was also observed
in the work of Park et al. [22] who conducted pyrolysis experiments on moisture free maple wood particles heated in a vertical
tube furnace at temperatures ranging from 638 to 879 K. However, their pyrolysis model with three parallel primary reactions
did not allow observation of this phenomenon. This is because
they did not account for the sensible heat released due to the
chemical decomposition of the virgin particle, and an endothermic
heat of 64 kJ/kg was assumed for all primary reactions. Therefore, they proposed a kinetic model according to which the virgin
biomass is decomposed to gas, tar and an intermediate solid as primary reactions, with secondary reactions including conversion of
the intermediate solid to char and cracking of tar to form additional gas and char. Despite that this model was not supported
by any experimental observations, however, as an endothermic
heat for primary gas and tar formation was used while an exothermic heat for char generation was considered, they were on a right
track since these considerations were consistent with ndings of
Milosavljevic et al. [34].
4.3. Comparison with data of Rath et al.
Fig. 4. Comparison of predicted mass loss and center temperature (lines) with
measurements of Koufopanos et al. [15] (symbols) at two reactor temperatures:
623 K (top), 773 K (bottom). () Measured temperatures; () measured mass losses;
) kinetic data of Chan et al.; (
) kinetic data of Thurner and Mann; (
)
(
kinetic data of Di Blasi and Branca.
151
Table 9
Validation of the model with experiments of Koufopanos et al. [15] (AVE: average relative error; SD standard deviation of relative error).
Thurner and Mann
Chan et al.
Tr [K]
AVE
SD
AVE
SD
AVE
SD
623
773
623
773
673
0.204
0.070
0.561
0.183
0.255
0.218
0.149
0.257
0.260
0.400
0.357
0.034
0.642
0.247
0.255
0.344
0.169
0.281
0.408
0.315
0.161
0.217
0.440
0.332
0.612
0.187
0.251
0.348
0.642
0.487
Fig. 5. Predicted temperature and biomass density proles at the center and the surface of the particle related to the experimental conditions of Koufopanos et al. [15] at
reactor temperature of 623 K.
152
Table 10
Validation of the model with experiments of Rath et al. [43] (AVE: average relative error; SD: standard deviation of relative error).
Thurner and Mann
AVE
SD
Chan et al.
Font et al.
Mass loss
Tr=0 [K]
Mass loss
Tr=0 [K]
Mass loss
Tr=0 [K]
Mass loss
Tr=0 [K]
0.383
0.374
0.027
0.19
0.205
0.243
0.017
0.202
0.224
0.147
0.006
0.251
0.62
0.555
0.052
0.172
Fig. 8. Comparison of the predicted center temperature and mass loss (lines) with
measurements of Rath et al. [43] (symbols); (
) kinetic data of Chan et al.; (
)
) kinetic data of Di Blasi and Branca; (
)
kinetic data of Thurner and Mann; (
kinetic data of Font et al.
Fig. 7. Comparison of the predicted mass loss and center temperature (lines) with
measurements of Koufopanos et al. [15] (symbols) at a reactor temperatures of 623 K
at three different values for the heat of reaction without accounting for the sensible
heat released due to the conversion of the virgin material to char and volatiles.
153
t
Fig. 9. Predicted temperature and biomass density proles at the center and the
surface of the particle related to the experimental conditions of Rath et al. [43].
5. Conclusions
Several conclusions can be drawn from this study. Comparison
of the simulation results with experimental data of large biomass
particles obtained at different process conditions reveals that the
thermo-kinetic model presented in this work provides satisfactory
predictions when the kinetic parameters of Chan et al. or Thurner
and Mann are employed. The pyrolysis model with three parallel reactions yielding tar, gas and char together with an extended
version of energy equation sufciently captures the experimental
observations of pyrolyzing biomass particles, such as the center
temperature peak reported in some past studies. These experimental validations clearly demonstrate the signicant inuence of the
amount of heat released during the conversion of virgin biomass
on the thermal degradation of the particle. Furthermore, the kinetic
model with three parallel reactions is sufcient to achieve a reasonable agreement between the predictions and experiments so that
any inclusion of secondary reactions is not needed.
A single value for the heat of primary reactions; i.e. 25 kJ/kg,
has been obtained in this work by assuming hBg = hBC and tting the predictions to the measurements. In fact, it represents a
lumped heat of volatiles and char formation at a reference temperature. Given that a satisfactory agreement between the simulations
and experimental data is achieved with the above endothermic
pi h i
1 n
1
(r ug h g ) = n
r n r
r r
r n k
T
r
i = B, C, g
(A.1)
all
h
[B h B + C h C + g h g ]
t
(B h B )
h B
B
= B
+ h B
t
t
t
(C h C )
h C
C
= C
+ h C
t
t
t
(g h g )
h g
g
= g
+ hg
t
t
t
Hence,
all
h
=
B
+
+
h B
B
+ h B
t
t
g
h g
t
+ h g
g
t
C
h C
C
+ h C
t
t
=
B cB
g
B
C
h B
+ h C
+ h g
t
t
t
T
T
T
+C cC
+g cg
t
t
t
(A.2)
154
h g
T
1 n
r ug
+ h g (r n ug ) = ug cg
+ h g n
(r ug )(A.3)
r r
r
r
r
n
all
1 n
h + n
(r ug h g )
r r
=
B cB
T
T
T
+ C cC
+ g cg
t
t
t
+
g
B
C
h B
+ h C
+ h g
t
t
t
T
T
B
C
= (B cB + C cC + g cg )
+ ug cg
+ h B
+ h C
+ h g
t
r
t
t
+ ug cg
T
1 n
+ h g n
(r ug )
r r
r
(A.4)
g
1 n
+ n
(r ug )
r r
t
g
1 n
+ n
(r ug ) = h B (k1 + k2 + k3 )B + h C (k3 B ) + h g (k1 + k2 )B (A.5)
r r
t
Inserting Eq. (A.5) into Eq. (A.4), and then substituting it into Eq.
(A.1), we get
(B cB + C cC + g cg )
T
T
1
+ ug cg
= n
r r
t
r
r n k
T
r
+ Q
(7)
[16]
[17]
[18]
where
Q
(A.6)
(A.7)
If a tar cracking reaction was also taken into account, Eq. (A.7) would
be as follows.
Q = B (k1 + k2 )[hBg +
(cT cG )dT ]
[26]
[27]
[28]
[30]
[31]
[32]
[24]
[25]
[29]
[19]
[20]
[21]
[22]
[23]
cp dT to read
(cB cC )dT ]
[11]
[12]
[13]
[14]
[15]
(8)
[33]
[34]
[35]
References
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[3] C. Di Blasi, Ind. Eng. Chem. Res. 35 (1996) 3746.
[4] M.G. Gronli, M.C. Melaaen, Energy Fuels 14 (2000) 791800.
[5] A. Bharadwaj, L.L. Baxter, A.L. Robinson, Energy Fuels 18 (2004) 10211031.
[6] J. Larfeldt, B. Leckner, M.C. Melaaen, Fuel 79 (2000) 16371643.
[7] A. Galgano, C. Di Blasi, Ind. Eng. Chem. Res. 42 (2003) 21012111.
[8] C.A. Koufopanos, G. Maschio, A. Lucchesi, Can. J. Chem. Eng. 67 (1989) 7584.
[9] F. Shazadeh, P.S. Chin, Chem. A: ACS Symp. Ser. 43 (1977) 5781.
[10] C. Di Blasi, Chem. Eng. Sci. 51 (1996) 11211132.
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]