Chemical Engineering Science 59 (2004) 1999 – 2012

www.elsevier.com/locate/ces

Heat transfer and kinetics in the pyrolysis of shrinking biomass particle

B.V. Babu∗ , A.S. Chaurasia
Department of Chemical Engineering and Engineering Technology, Engineering Services Division (ESD), Birla Institute of Technology and Science
(BITS), Pilani, Rajasthan 333031, India
Received 25 May 2003; received in revised form 4 January 2004; accepted 15 January 2004

Abstract

The impact of shrinkage on pyrolysis of biomass particles is studied employing a kinetic model coupled with heat transfer model
using a practically signi0cant kinetic scheme consisting of physically measurable parameters. The numerical model is used to examine
the impact of shrinkage on particle size, pyrolysis time, product yields, speci0c heat capacity and Biot number considering cylindrical
geometry. Finite di4erence pure implicit scheme utilizing tri-diagonal matrix algorithm (TDMA) is employed for solving heat transfer
model equation. Runge–Kutta fourth-order method is used for chemical kinetics model equations. Simulations are carried out for radius
ranging from 0.0000125 to 0:05 m, temperature ranging from 303 to 900 K and shrinkage factors ranging from 0.0 to 1.0. The results
obtained using the model used in the present study are in excellent agreement with many experimental studies, much better than the
agreement with the earlier models reported in the literature. Shrinkage a4ects both the pyrolysis time and the product yield in thermally
thick regime. However, it is found that shrinkage has negligible a4ect on pyrolysis in the thermally thin regime. The impact of shrinkage
re9ects on pyrolysis in several ways. It includes reduction of the residence time of gases within the particle, cooling of the char layer due
to higher mass 9ux rates of pyrolysis products and thinning the pyrolysis reaction region.
? 2004 Elsevier Ltd. All rights reserved.

Keywords: Modelling; Simulation; Kinetics; Heat transfer; Pyrolysis; Shrinkage

1. Introduction
There has been a growing interest in the renewable energy
sources since the last two decades. The understanding of
the interaction between chemical and physical mechanisms
during solid pyrolysis is of fundamental importance, for the
optimal design of chemical pyrolysis reactors and combus-
tors. The shrinking of the solid particle a4ects the pyrolysis
in several ways. The medium properties (porosity, perme-
ability, density, mass di4usivity, speci0c heat capacity and
thermal conductivity), the volume occupied by the volatiles
(gas and tar), the volume occupied by the solid (wood and
char), and consequently the total volume of the particle also
changes continuously. As a result of the chemical restructur-
ing during pyrolysis, the density of the char increases. The
temperature pro0le of the particle changes due to increased
density and decreased distance across the pyrolysis region.
∗
Corresponding author. Tel.: +91-1596-245073, Ext. 205/224;
fax: +91-1596-244183.
E-mail address: bvbabu@bits-pilani.ac.in (B.V. Babu).
URL: http://bvbabu.50megs.com
The product yield is also a4ected by the thinner and hotter
char layer. In the present study, the model developed and
modi0ed by Babu and Chaurasia (2003a,b, 2004a,b,c) is ex-
tended using physically measurable parameters and practi-
cally explainable kinetic scheme proposed by Koufopanos
et al. (1991), which is not used by earlier researchers to
study the impact of shrinkage on the pyrolysis of biomass.
2. Background
Several researchers have developed models for biomass
pyrolysis (Bamford et al., 1946; Fan et al., 1977; Miyanami
et al., 1977; Chan et al., 1985; Ragland et al., 1988; Alves
and Figueiredo, 1989; Saastamoinen, 1993; Di Blasi, 1994,
1995, 1996a,b; Melaaen and GrHnli, 1997; Bryden et al.,
2002; Hagge and Bryden, 2002). Many of these models do
not include the impact of shrinkage on the pyrolysis pro-
cess. It is based on the assumption that the total volume
of the particle does not change during thermal degradation.
On the other hand, experiments conducted for large biomass
particles (Lee et al., 1976; Chan et al., 1988) have shown
signi0cant shrinkage of char layer as the pyrolysis front

0009-2509/$ - see front matter ? 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.01.050
2000 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012
propagates through the solid. Morel et al. (1990) have mod-
eled the changes in particle size due to disintegration of
the solid structure at some critical conversion during char
gasi0cation. Villermaux et al. (1986) described the shrink-
age e4ects assuming that the solid density remains constant
as degradation occurs. They considered a very simpli0ed
one-step reaction model, and the secondary reactions are not
accounted for.
The actual reaction scheme of pyrolysis of biomass is ex-
tremely complex because of formation of over a hundred in-
termediate products. Pyrolysis of biomass is, therefore, gen-
erally modeled on the basis of apparent kinetics. Di4erent
kinetic schemes are used by various researchers, some of
which are given below.
Kinetic scheme-1: The chemical processes of biomass py-
rolysis are described through a primary and a secondary
stage (Sha0zadeh and Chin, 1977; Thurner and Mann, 1981;
Chan et al., 1985; Font et al., 1990) as follows:
Wood k4
k1 k2 k3 Tar
Gas Tar Char k5
Wood undergoes thermal degradation according to pri-
mary reactions (k1 ; k2 ; k3 ) giving gas, tar and char as prod-
ucts. Tar may undergo secondary reactions (k4 , k5 ).
Kinetic scheme-2:
k4
k1 k3 Tar
Cellulose Active cellulose
k2 Char + Gas
This is the Broido–Sha0zadeh scheme of cellulose py-
rolysis (with kinetic constants k1 ; k2 , and k3 as in Bradbury
et al., 1979), extended to include secondary reaction with
kinetic constant k4 (Liden et al., 1988) in which the forma-
tion of ‘active’ cellulose precedes the formation of gas, tar
and char.
Kinetic scheme-3:
Virgin biomass B ( n1 order decay)
Reaction 1 Reaction 2
(Volatile + Gases)1 + (Char)1
( n 2 order decay) ( n3 order decay)
Reaction 3
(Volatile + Gases)2 + (Char)2
This kinetic scheme is proposed by Koufopanos et al.
(1991), in which the biomass decomposes to volatiles, gases
and char. The volatiles and gases may further react with
char to produce di4erent types of volatiles, gases, and char
where the compositions are di4erent. Therefore, the primary
pyrolysis products participate in secondary interactions (Re-
action 3), resulting in modi0ed 0nal product distribution.
Di Blasi (1996a) and Hagge and Bryden (2002) utilized
the kinetic scheme-1 while studying the impact of shrink-
age on the pyrolysis of biomass. The main drawback of this
kinetic model as pointed out by Di Blasi (2000) is that it
is based on the assumption of a constant ratio between the
yields of solid char and volatile products. Therefore, it is not
applicable for fast pyrolysis and for predicting the product
distribution. Consequently, it cannot predict the dependence
of product yields on reactor temperature and heating rate,
which is of fundamental importance in reactor design and
operation. The kinetic constants k1 , k2 , and k3 of primary
reactions and k4 and k5 of secondary reactions should corre-
spond to the same wood sample. However, Di Blasi (1996a)
and Hagge and Bryden (2002), in their studies, took the ki-
netic constants of primary reactions (k1 ; k2 ; k3 ) from Thurner
and Mann (1981), Chan et al. (1985) and Font et al. (1990),
while the kinetic constants for secondary reactions (k4 and
k5 ) from Liden et al. (1988) and Di Blasi (1993), respec-
tively. In fact, the wood samples used for the above primary
Gas
and secondary reactions in the above references are not of
same type.
A recent re-examination (Varhegyi et al., 1994) of the
Char Broido–Sha0zadeh scheme (kinetic scheme-2) of cellulose
pyrolysis (with kinetic constants k1 , k2 , and k3 as in Bradbury
et al., 1979), extended to include secondary reactions with
kinetic constant k4 (Liden et al., 1988) has raised some ques-
tions about the importance of the initiation reaction leading
to the formation of ‘active’ cellulose intermediate. More pre-
cisely, new kinetic measurements seem to indicate that such
a reaction is super9uous in the temperature range of 523 to
Gas 643 K. Even rough estimations of kinetic data for the for-
mation of an intermediate ‘active’ wood are not available.
Keeping the above drawbacks of kinetic scheme-1 and -2
in mind, the kinetic scheme-3 proposed by Koufopanos et al.
(1991) and also utilized successfully by Babu and Chaurasia
(2003a,b) in their earlier studies is used in the present study
also. Koufopanos et al. (1991) have determined both pri-
mary and secondary reaction rate constants and heat of py-
rolysis by matching models with measured mass loss and
temperature pro0le data. This approach is to be favored since
it enhances the reliability of model predictions.
3. Description of mathematical model
In the present study, a biomass particle of cylindrical
shape of radius R, length l and radial thickness dr is con-
sidered. The length/diameter ratio of 5 is considered to be
high enough to assume that the cylinders approximate bod-
ies with an in0nite axial length (Tye, 1969), so that heat
transfer takes place in radial direction only. It is assumed
that heat 9ows in one dimension and that heat transfer inside
the particle occurs by conduction only. The heat transfer
coeJcient represents the overall e4ect of the above mecha-
nisms. The chemical kinetics and heat transfer model equa-
tions (1)–(9) along with initial and boundary conditions are
 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012 2001

Table 1
Mathematical model

Koufopanos et al. (1991) mechanism

Virgin biomass B ( n1 order decay)

Reaction 1 Reaction 2

Reaction 3
(Volatile + Gases) 1 + (Char)1 (Volatile + Gases)2 + (Char)2
( n 2 order decay) ( n3 order decay)
Particle model

Conservation of biomass, (gases and volatiles)1 , (char)1 , (gases and volatiles)2 and (char)2 :

@(CB V ) n
= −(k1 + k2 )CB1 V (1)
@t
@(CG1 Vg ) n n2 n
= k1 CB1 V − k3 CG1 Vg CC13 V (2)
@t
@(CC1 V ) n n2 n
= k2 CB1 V − k3 CG1 Vg CC13 V (3)
@t
@(CG2 Vg ) n2 n
= k3 CG1 Vg CC13 V; (4)
@t
@(CC2 V ) n2 n
= k3 CG1 Vg CC13 V (5)
@t
Enthalpy:



@ b − 1 @T @2 T @
(Cp T ) = k + + (−LH ) − (6)
@t r @r @r 2 @t
Initial conditions:

t = 0; CB = CB0 ; CG1 = CC1 = CG2 = CC2 = 0; V = VB0 ; Vg = 0:5VB0 ; T (r; 0) = T0 (7)

Particle boundary conditions:


@T
t ¿ 0; r = 0; =0 (8)
@r r=0


@T
t ¿ 0; r = R; ke4 = h(Tf − T ) + (Tf4 − T 4 ) (9)
@r r=R
Dimensionless forms of Eqs. (1)–(9):

@(CM B VM ) n
= −(k1 + k2 )CM B1 VM (10)
@t
@(CM G1 VM g ) n n2 M M n3 M
= k1 CM B1 VM − k3 CM G1 V g C C1 V (11)
@t
@(CM C1 VM ) n n2 M M n3 M
= k2 CM B1 VM − k3 CM G1 V g C C1 V (12)
@t
@(CM G2 VM g ) n2 M M n3 M
= k3 CM G1 V g C C1 V (13)
@t
@(CM C2 VM ) n2 M M n3 M
= k3 CM G1 V g C C1 V (14)
@t
@ b − 1 @ @2  Q R2 k1
= + + (15)
@ x @x @x2 
 = 0; CM B = 1; CM G1 = CM C1 = CM G2 = CM C2 = 0; VM = 1; VM g = 0:5; (x; 0) = 1 (16)

@
 ¿ 0; x = 0; =0 (17)
@x
@
 ¿ 0; x = 1; = −H (18)
@x
2002 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012

Table 1 Continued.

Equations describing the time evolution for VS , Vg and V :

VS MB   MC
= + (19)
VS0 MB0 MB0
Vg = Vg0 +  (V − VS ) (20)
S0

Vg0 = !Vgi + (1 − !)Vgf (21)

Vgf = # Vgi (22)

V = Vg + VS (23)

VM = V=VS0 (24)

VM g = Vg =VS0 (25)

Koufopanos et al. (1991) correlation:

h = 0:322(k=l)Pr 1=3 Re0:5 (26)

Other relations:

 = Vg =V; ! = MB =MB0 (27,28)

Table 2 by Eqs. (19)–(23). As the pyrolysis progresses, the vol-

Dimensionless groups ume occupied by the solid is assumed to decrease linearly
 = k=Cp (29) with the wood mass and to increase with the char mass, by
a chosen shrinkage factor, 
given by Eq. (19). The vol-
x = r=R (30) ume of volatiles is made up of two contributions. As given
 = t=R2 (31)
by Eq. (20), the 0rst Vg0 is the initial volume occupied by
volatiles, and the second term
(VS0 − VS ) is the fraction
 = (T − Tf )=(T0 − Tf ) (32) of volume left by the solid as a consequence of the pyrol-
ysis process. To consider the structural changes that take
H = (R=ke4 )[h + (T 3 + T 2 Tf + Tf2 T + Tf3 )] (33)
place during the pyrolysis, Vg0 may also vary linearly with
Bi = hR=ke4 (34) the composition of the degrading medium. It varies from
an initial value, Vgi , determined by the initial solid porosity,
Q = (−LH + Cp T )=(Cp (T0 − Tf )) (35) to a 0nal value taken as a fraction, #
, of the initial one as
Q =
n
QCB1 (36) given by Eqs. (21) and (22). The total particle volume is
expressed by Eq. (23). The value of the parameters 
,

CM B = CB =CB0 (37) and #
vary from 0.0 for total disintegration of the particle
to 1.0 for no shrinkage.
CM B0 = CB0 =0 (38)

CM G1 = CG1 =CB0 (39)

CM C1 = CC1 =CB0 (40) 4. Numerical solution and simulation

CM G2 = CG2 =CB0
CM C2 = CC2 =CB0
given in Table 1. The dimensionless forms of Eqs. (1)–(9)
are given by Eqs. (10)–(18) with the dimensionless groups
as given in Table 2 (Eqs. (29)–(42)).
The time evolution for solid, gases and volatiles, and to-
tal volumes of the particle (VS , Vg and V ) are described
(41) Eq. (15) along with initial and boundary conditions
given by Eqs. (16)–(18) are solved numerically by 0nite
(42)
di4erence method using pure implicit scheme. Pure im-
plicit scheme is an unconditionally stable scheme, i.e.,
there is no restriction on time step in sharp contrast
with Euler and Crank-Nicholson method as discussed by
Ghoshdastidar (1998). Eqs. (10)–(15) are solved simul-
taneously. Eqs. (10)–(14) are solved by Runge–Kutta
fourth-order method with both 0xed step size and variable
step size. It is found that Runge–Kutta fourth-order vari-
able step-size method (RKVS) is faster than Runge–Kutta
 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012 2003

Table 3
Values and correlations used in the numerical solution of the model

Property Correlation/value Source

Convective heat transfer coeJcient h = 8:4 W m−2 K −1 Pyle and Zaror (1984)
Wood speci0c heat capacity Cp = 1112:0 + 4:85(T − 273) (J kg−1 K −1 ) Koufopanos et al. (1991)
Char speci0c heat capacity Cp = 1003:2 + 2:09(T − 273) (J kg−1 K −1 ) Koufopanos et al. (1991)
E4ective thermal conductivity ke4 = !kB + (1 − !)kC Chan et al. (1985)
+ kg + 13:5T 3 d= (W m−1 K −1 )
Wood thermal conductivity kB = 0:13 + 0:0003(T − 273) (W m−1 K −1 ) Koufopanos et al. (1991)
Char thermal conductivity kC = 0:08 − 0:0001(T − 273) (W m−1 K −1 ) Koufopanos et al. (1991)
Gas thermal conductivity kg = 25:77 × 10−3 (W m−1 K −1 ) Di Blasi (1993)
Pore diameter d = 2 × 10−5 (m) Di Blasi (1996a)
Emissivity coeJcient  = 0:95 Pyle and Zaror (1984)
Rate constant of reaction 1 k1 = A1 exp[(D1 =T ) + (L1 =T 2 )] (s−1 ), Koufopanos et al. (1991)
where A1 = 9:973 × 10−5 s−1 ,
D1 = 17254:4 K; L1 = −9061227 K 2
Rate constant of reaction 2 k2 = A2 exp[(D2 =T ) + (L2 =T 2 )](s−1 ), Koufopanos et al. (1991)
where A2 = 1:068 × 10−3 s−1 ,
D2 = 10224:4 K; L2 = −6123081 K 2
Rate constant of reaction 3 k3 = A3 exp[(−E3 =Rc T )](s−1 ), Koufopanos et al. (1991)
where A3 = 5:7 × 105 s−1 ,
E3 = 81000 J mol−1
Heat of reaction LH = −255000 J kg−1 Koufopanos et al. (1991)
Initial density of wood 0 = 650 kg m−3 Koufopanos et al. (1991)
Initial thermal di4usivity of wood  = 1:79 × 10−7 m2 s−1 Jalan and Srivastava (1999)
Initial void fraction of particle  = 0:5 Fan et al. (1977)

fourth-order method with 0xed step size (RKFS), as dis-
cussed by Babu et al. (2004). But RKVS method does not
give the solution for a particular and 0xed interval of time.
Hence, to obtain the solution at a particular interval of time,
which is required to compare results of present study with
those reported in literature, RKFS method is used in the
present study. The discretized form of Eq. (15) is solved
by tri-diagonal matrix algorithm (TDMA) also known as
Thomas Algorithm (Carnahan et al., 1969).
Simulations are carried out for cylindrical geometry
considering radius ranging from 0.0000125 to 0:05 m, and
temperature ranging from 303 to 900 K. The values of the
parameters 
,
and #
can be varied from 0.0 which rep-
resents total shrinkage to 1.0 which represents no shrinkage
of the particle. Extensive simulations have been carried by
varying the values of these parameters between 0.0 and 1.0
with di4erent combinations. It is found that for 
= 0:2,


=0:0 and #
=0:2 which nearly represents the total shrink-
age of the particle, the model is in excellent agreement with
many experimental results (Sha0zadeh et al., 1979; Pyle
and Zaror, 1984; Scott et al., 1988). Hence, same values
of the parameters are retained for all the simulations in
the present study. The choice of lower possible values of
shrinkage factor (
= 0:2;
= 0:0; #
= 0:2) in the present
study is more realistic of incorporating shrinkage e4ect as
against relatively higher values (
= 0:5;
= 0:0; #
= 0:5)
as taken by Di Blasi (1996a). It may be noted that Hagge
and Bryden (2002) in their study considered the shrinkage
due to char only, and they did not consider the shrinkage
due to the volume occupied by the volatiles as discussed
by Di Blasi (1996a). This limitation is also recti0ed in the
present study. The values of various parameters employed
in the present study are listed in Table 3. Initial e4ective
solid volume (VS0 ) is taken as half of the initial biomass
concentration (VB0 ).
5. Results and discussion
5.1. Models’ validation and comparison
The model is validated with a wide range of experimen-
tal results reported in the literature. Some of the typical
results are presented here. Fig. 1 shows the temperature
pro0le as a function of time at the center (i.e., x = 0) of the
cylindrical pellet of radius 0:003 m for 0nal temperature
of 780 K. This is compared with pro0les obtained by the
model of Jalan and Srivastava (1999), the model of Babu
and Chaurasia (2003a) without shrinkage and the experi-
mental data obtained by Pyle and Zaror (1984). It is found
that the present model results with shrinkage are in excel-
lent agreement with the experimental data better than the
agreement with the model of Jalan and Srivastava (1999)
and the model of Babu and Chaurasia (2003a). The present
model predicts better even for particle radius of 0:0075 m
as compared to the other models as shown in Fig. 2. As is
evident from Figs. 1 and 2, the earlier models underpredict
the experimental data at higher values of pyrolysis time,
while the present model predictions match excellently well
for the entire duration of pyrolysis time. This explains the
importance of shrinkage e4ect that is being incorporated in
2004 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012

1000
100 Pyle & Zaror (1984) (Experimental)
Pyle & Zaror (1984) (Experimental)
Present model results with shrinkage Present model results with shrinkage
900 90
Babu & Chaurasia model results without shrinkage (2003a) Babu & Chaurasia model results without shrinkage (2003a)
Jalan & Srivastava model (1999) 80 Liliedahl & Sjostrom model (1998)
800
70

Conversion (%)
Temperature (K)

700 60

50
600
40

500 30

20
400
10

300 0

0 20 40 60 80 100 0 50 100 150 200 250 300

Time (s) Time (s)

Fig. 1. Temperature pro0le as a function of time at the centre of the Fig. 4. Conversion pro0le as a function of time with cylindrical pellet
cylindrical pellet (R = 0:003 m; T0 = 303 K; Tf = 780 K; x = 0). (R = 0:011 m; T0 = 303 K; Tf = 753 K).

the present model. Fig. 3 shows the temperature pro0les as a

700 function of dimensional radial distance for the 0nal temper-
Pyle & Zaror (1984) (Experimental) ature of 643 K after 11 min. The temperature pro0les ob-
Present model results with shrinkage
Babu & Chaurasia model results tained using present model with shrinkage are in much bet-
600 without shrinkage (2003a) ter agreement with the experimental data of Pyle and Zaror
Jalan & Srivastava model (1999)
(1984) when compared to the other three models. The
Temperature (K)

500
present model predictions are in excellent agreement with
experimental data, substantiating the shrinkage e4ect, for
the entire range of dimensionless distance (from center to
400 the surface) of the particle, while the earlier models under-
predict all through the distances from center to surface of
the particle.
300 The model developed is also compared with the model of
Liliedahl and SjRostrRom (1998) as shown in Fig. 4. The con-
0 20 40 60 80 100 120 140 160 version pro0le as a function of time with cylindrical pellet
Time (s)
of radius 0:011 m and 0nal temperature of 753 K is shown
Fig. 2. Temperature pro0le as a function of time at the centre of the in Fig. 4. As can be seen from 0gure, the model developed
cylindrical pellet (R = 0:0075 m; T0 = 303 K; Tf = 773 K; x = 0). is in better agreement as compared to the model of Liliedahl
and SjRostrRom (1998), while the latter underpredicts the con-
version at higher values of pyrolysis time. This may be
due to the fact that while developing the model, Liliedahl
700
and SjRostrRom (1998) did not consider thermal conductivity
and speci0c heat capacity of biomass as a function of tem-
perature, and also did not incorporate the shrinkage e4ect.
600
As shown in Fig. 5, the inclusion of shrinkage signi0cantly
improves the modeling results when validated with the ex-
Temperature (K)

perimental data of Scott et al. (1988) and Sha0zadeh et al.

500
Pyle & Zaror (1984) (Experimental)
Present model results with shrinkage
Babu & Chaurasia model results without shrinkage (2003a)
400
Jalan & Srivastava model (1999)
Bamford, Crank & Malan model (1946)
300
0.0 0.2 0.4
Radial distance (-)
Fig. 3. Temperature pro0le as a function of radial distance with cylindrical
pellet (R = 0:011 m; T0 = 303 K; Tf = 643 K; t = 11 min).
(1979).
The values are given in Tables 4 and 5 also for quanti-
tative comparison of present model with shrinkage with the
earlier models and the literature data. The average percent-
age error and standard deviation are also calculated. If Yexp
is the experimental value of a quantity and Ycal is the value
obtained from the modeling equation, then average percent-
0.6 0.8 1.0
age error Epa is de0ned as follows:
N
[(Yexp − Ycal )=Yexp ] ∗ 100
Epa = i=1 : (43)
N
 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012 2005

15 Table 5
Babu & Chaurasia model results without shrinkage (2003a) Comparison of present model results with shrinkage with those of earlier
Present model results with shrinkage models for pyrolysis time = 11 min (R = 0:011 m; T0 = 303 K; Tf =
Shafizadeh et al. (1979) (Experimental)
643 K)
Scott et al. (1988) (Experimental)
10 x Temperature (K)

PZ PS BC JS BCM
Yield (%)

0 643 637 619 612 605

5 0.3 643 638 620 614 605
0.5 643 639 623 617 605
0.7 643 640 627 622 600
0.9 643 642 632 620 595

0 Epa 0.59 2.92 4.04 6.38

600 650 700 750 800 850 900
SD 0.0073 0.0337 0.0457 0.0716
Temperature (K) PZ= Pyle and Zaror (1984) (experimental); PS=present model with
shrinkage; BC=Babu and Chaurasia’s (2003a) model; JS= Jalan and
Fig. 5. Average char yield as a function of temperature for particle Srivastava’s (1999) model; BCM= Bamford et al. (1946) model.
half-thickness of 0:0000125 m.

sity have already been discussed by the present authors in

Table 4 their earlier studies (Babu and Chaurasia, 2002a,b, 2003c,d;
Comparison of present model results with shrinkage with those of earlier
Chaurasia and Babu, 2003a,b). In the present study, the nu-
models for various stages of pyrolysis (time) at the center of cylindrical
pellet (R = 0:003 m; T0 = 303 K; Tf = 780 K) merical model is used to examine the impact of shrinkage
on particle size, pyrolysis time, product yields, speci0c heat
Time (s) Temperature (K) capacity and Biot number. The radius of cylinder considered
PZ PS BC JS ranges from 0.0000125 to 0:05 m. The temperatures range
considered from 303 to 900 K.
0 303 303 303 303
The excellent agreement between the present model pre-
10 365 363 366 362
20 466 465 473 459 dictions with the experimental data reported in the literature
40 642 618 619 598 much better than the earlier models as discussed in above
60 726 741 696 679 section consolidates the model validity for wide range of op-
70 769 766 719 704 erating conditions. Hence, extensive simulations have been
80 777 777 736 723
carried out for cylindrical geometry. In case of kinetically
90 786 781 748 736
controlled reaction (very small particle sizes), intra-particle
Epa 0.94 3.26 4.68 activity of secondary reactions is negligible even at high re-
SD 0.0165 0.0424 0.0600 action temperatures. Since the main objective of this study
PZ= Pyle and Zaror (1984) (experimental); PS=present model with
is to understand the impact of shrinkage, only the case of
shrinkage; BC=Babu and Chaurasia’s (2003a) model; JS= Jalan and heat-transfer-controlled conversion (thermally thin and thick
Srivastava’s (1999) model. regimes) is considered.

5.2.1. E6ect on particle size

Fig. 6 shows the temperature pro0le during pyrolysis of
The standard deviation (SD) is calculated by the following
a thermally thin cylindrical particle of radius 0:00025 m ex-
formula:
 1=2 posed to a 0nal temperature of 900 K. The temperature at
N 2
i=1 [(Y exp − Y cal )=Y exp ] the center and the surface of the particle is found to be uni-
SD = : (44) form. As expected, there is a very little di4erence between
N −1
the case in which shrinkage is considered and the case in
In all the cases, it is found that the average percentage error which shrinkage is not considered. In this case, there is no
and standard deviation from experimental data are signi0- char insulating the unreacted core. As a consequence, the
cantly less with the model developed in the present study as shrinkage has a minor impact on pyrolysis time and product
compared to the other models (see Tables 4 and 5). yield. The pyrolysis time for both the cases is found to be
5:5 s. In the pyrolysis of thermally thin particle, the resis-
5.2. Simulation results tance to heat transfer within the particle is small compared to
the external heat transfer. Thus, there is little residence time
The e4ect of particle size, orders of reaction, heat of re- for volatiles and gases within the particle, and the secondary
action, thermal conductivity, reactor temperature and den- pyrolysis reactions have a little impact on the product yield.
2006 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012

1000 particle. There is a di4erence more than 50 K in tempera-

900
0.00025 m ture between the shrinking and non-shrinking particle at the
800
0.0 m surface. As the char layer begins to develop, the shrinking
char layer allows a more rapid internal heat transfer. The
700
increase in the rate of internal heat transfer increases the
Temperature (K)

600 interior temperature of the particle. The higher temperature

500 values within the shrinking particle increase the rate of pri-
400 mary pyrolysis reactions thus reducing the time for comple-
tion of pyrolysis. The pyrolysis conversion time is found to
300
be 538 s for shrinking particle as compared to 585 s for the
Present model results with shrinkage
200
Babu & Chaurasia model results without shrinkage (2003a) non-shrinking particle. It is interesting to note from Fig. 7
100 that for the shrinking particle there is a dip (slight decrease
0 and then increase) in temperature for particle at the surface
0 1 2 3 4 5 6
(at the radial position of 0:02 m) at a time of 350 s, the
Time (s)
phenomenon of which is not observed for any other radial
Fig. 6. Temperature pro0le as a function of time with cylindrical pellet position of the particle from center to the surface. In order
for di4erent radial position (R = 0:00025 m; T0 = 303 K; Tf = 900 K). to understand this typical phenomenon, further simulations
are carried out at the surface of the particle of di4erent sizes
(radii) ranging from 0.00025 to 0:05 m.
1000 Up to a particle radius of 0:014 m, this dip is not observed
900 at the surface of the particle. Not having this dip in temper-
800 0.02 m
ature at the surface of the particle for smaller sizes can also
be seen from Fig. 6, where the results for a particle radius
700 0.016 m
of 0:00025 m are plotted. But, for a particle radius greater
Temperature (K)

600
500
400
0.004 m
0.0 m
300 0.008 m
200
Present model results with shrinkage
100
Babu & Chaurasia model results without shrinkage (2003a)
0 ysis time. The higher pyrolysis rates are due to the higher
0 100 200 300 400 500
Time (s)
Fig. 7. Temperature pro0le as a function of time with cylindrical pellet
for di4erent radial positions (R = 0:02 m; T0 = 303 K; Tf = 900 K).
In thermally thick pyrolysis, the relative rates of internal
and external heat transfer are similar. The particle temper-
ature is not uniform throughout as for the thermally thin
regime. The thin pyrolysis region separates the unreacted
core, which is surrounded by the char layer. As the pyrol-
ysis progresses, the char layer grows at the expense of the
unreacted core. The heat transfer to the unreacted core re-
duces due to the insulation of the char layer around the par-
ticle. Shrinkage of the char layer causes a sharper temper-
ature gradient, increases heat transfer to the interior of the
particle and cause a raise in the pyrolysis temperatures.
Fig. 7 shows the temperature pro0le as a function of time
for a 0:04 m particle (0:02 m radius) exposed to a 0nal tem-
perature of 900 K for di4erent radial positions. The tem-
perature of the shrinking particle (present model results)
is more than non-shrinking particle (Babu and Chaurasia,
2003a) at any radial position. The increase in temperature is
less near the center of the particle than at the surface of the
0.012 m than 0:014 m this dip in temperature (we call it a ‘thermal
wave’) is observed for the shrinking particle. This occurs
because of two factors. First, there is less insulation from
the char between the cold unreacted center and the surface.
Second, the higher pyrolysis rates result in higher 9ux rates
of pyrolysis products, providing additional cooling for the
char layer and reducing the temperature after certain pyrol-
600 heat transfer rate to the core of the particle, resulting in an
increased overall production rate of pyrolysis products in
the shrinking particle. As a larger exterior char layer devel-
ops in the non-shrinking particle, the char layer insulates the
particle. This reduces the heat transfer to the non-shrinking
particle relative to the shrinking particle. So, the rate of pro-
duction of pyrolysis products is less, causing no additional
cooling for the char layer and hence no ‘thermal wave’ is
observed in the non-shrinking particle. As the particle radius
increases (0:025 m) the impact of shrinkage increases, re-
sulting in an increase in the number of thermal waves. The
secondary thermal wave near the end of pyrolysis is a result
of the increase in primary pyrolysis production at the center
of the particle, as shown in Fig. 8. The number of thermal
waves increases further, for the larger size particles.
5.2.2. E6ect on pyrolysis time
Figs. 9 and 10 summarize the impact of shrinkage on the
pyrolysis time. The e4ects of shrinkage increase with par-
ticle size and the 0nal temperature. The thicker char layer
is formed for larger particle sizes. The internal resistance to
heat transfer for the unreacted core reduces as a result of
shrinkage by reducing the insulating e4ect of the char. This
 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012 2007

900 K
1000 1.0

Yield of (gases & volatiles)1 [mass fraction]

750 K

800 0.8 600 K

Temperature (K)

600 0.6

400 0.4
Present model results with shrinkage
Babu & Chaurasia model results without shrinkage (2003a)
200 0.2

Present model results with shrinkage

0 0.0 Babu & Chaurasia model results without shrinkage (2003a)

0 100 200 300 400 500 600 700 800 900 1E-4 1E-3 0.01 0.1
Time (s) Particle Thickness (m)

Fig. 8. Temperature pro0le as a function of time with cylindrical pellet Fig. 11. Yield of (gases and volatiles)1 as a function of particle ra-
at the surface of the particle (R = 0:025 m; T0 = 303 K; Tf = 900 K). dius with cylindrical pellet for di4erent values of 0nal temperatures
(T0 = 303 K).

100
Present model results with shrinkage increases the importance of the char layer and hence the im-
Babu & Chaurasia model results without shrinkage (2003a) portance of shrinkage. As shown in Fig. 9, shrinkage does
80 not have a signi0cant e4ect on pyrolysis time, as the parti-
cle radius is small (0:001 m). The pyrolysis time decreases
60
as the temperature is increased. There is very less di4erence
(¡ 1 s) in the pyrolysis time between the shrinking and the
Time (s)

non-shrinking particle. As the particle radius increases to

40
0:02 m, the impact of shrinkage on pyrolysis time is ob-
served as shown in Fig. 10. As the shrinkage reduces the
20 insulating a4ect of the char, the pyrolysis time reduces by
more than 50 s for all the external temperatures as compared
0 to the non-shrinking particle. Reduction in pyrolysis time
700 750 800 850 900 950
implies the higher pyrolysis rates due to higher heat transfer
Temperature (K) rate from shrinked surface to the core of the particle. This
results in an increased overall production rate of pyrolysis
Fig. 9. Pyrolysis times as a function of temperature with cylindrical pellet products in the shrinking particle as also mentioned in the
(R = 0:001 m; T0 = 303 K). previous section.

5.2.3. E6ect on product yield

Babu & Chaurasia model results without shrinkage (2003a)
The impact of shrinkage on pyrolysis products is shown
1000
Present model results with shrinkage in Figs. 11–13. Extensive simulations are carried out for
both shrinking and non-shrinking particles for particle radius
900
ranging from 0.0001 to 0:05 m for di4erent 0nal tempera-
tures. Shrinkage favors high rates of heat transfer from the
800
shrinked surface towards the interior of the solid and large
Time (s)

pyrolysis temperatures are attained. Shrinkage a4ects the

700 pyrolysis in several ways. It includes reduction of the resi-
dence time of volatiles and gases within the particle, cooling
600 of the char layer due to higher mass 9ux rates of pyroly-
sis products, and thinning of the pyrolysis reaction region.
500 This e4ect favors the formation of (volatiles and gases)1 (as
in Fig. 11) at the expense of the decrease in formation of
700 750 800 850 900 950
Temperature (K)
(char)1 (as in Fig. 12) and (volatiles and gases)2 or (char)2
(as in Fig. 13). As the surface temperature increases from
Fig. 10. Pyrolysis times as a function of temperature with cylindrical 600 to 900 K, the yield of (char)1 (as in Fig. 12) decreases
pellet (R = 0:02 m; T0 = 303 K). while the yield of (volatiles and gases)1 (as in Fig. 11)
2008 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012

0.5 Present model results with shrinkage 1.0 600

Babu & Chaurasia model results without shrinkage (2003a)
0.9
500
0.8
Yield of (char)1 [mass fraction]

0.4
0.7

Product yields (-)

400

Pyrolysis time (s)

LEGEND
0.6 Pyrolysis time
0.3
0.5 (Volatile & Gases)1 300
(Char)1
0.4 (Char)2 or (Volatile & Gases)2
0.2 200
600 K 0.3
0.2
100
0.1 750 K
0.1

900 K 0.0 0

0.0
1 2 3 4 5
1E-4 1E-3 0.01 0.1 Specific heat capacity (kJ/kgK)

Particle Thickness (m)

Fig. 14. Final product yields and pyrolysis time as functions of speci0c
Fig. 12. Yield of (char)1 as a function of particle radius with cylindrical heat capacity with cylindrical pellet as simulated using present model
pellet for di4erent values of 0nal temperatures (T0 = 303 K). with shrinkage (R = 0:02 m; T0 = 303 K; Tf = 900 K).
Yield of (gases & volatiles)2 or (char)2 [mass fraction]

Present model results with shrinkage

0.5
Babu & Chaurasia model results without shrinkage (2003a)
0.4
0.3
0.2
0.1
0.0
1E-4
Fig. 13. Yield of (gases and volatiles)2 as a function of particle ra-
dius with cylindrical pellet for di4erent values of 0nal temperatures
(T0 = 303 K).
increases. As shown in Fig. 12, the production of (char)1
decreases with increase in temperature and increases with
particle size. It may be due to a small amount of repoly-
merization as mentioned by Hagge and Bryden (2002). Sec-
ondary reactions occur as volatiles and gases 9ow through
the char layer. Secondary char formation is negligible (re-
fer Fig. 13) due to very low reaction rate for the deposition
of volatiles and gases onto the char layer. This is due to the
fact that the residence time of volatiles and gases is much
less in the shrinking particle.
Non-shrinking particles favor the formation of (char)1
(as in Fig. 12) and (volatiles and gases)2 or (char)2 (as in
Fig. 13) at the expense of decrease in (volatiles and gases)1
formation (as in Fig. 11). This is due to the high residence
time of volatiles and gases within the particle, thicker char
layer and slow rates of formation of pyrolysis products. The
yield of (volatiles and gases)1 (as in Fig. 11) decreases up
to a particle radius of 0:015 m and then again increases at
the expense of decrease in (char)1 formation (as in Fig. 12)
for the 0nal temperature of 750 and 900 K. This is a con-
900 K
sequence of successively higher temperatures at the surface
due to an increase in the pyrolysis time as particle size is
750 K
increased. This trend is not observed for 600 K, as the tem-
perature is less (¡ 673 K). For this case, the reduction in
degree of polymerization is dominant, and hence di4usion
and convection e4ects are negligible (Sha0zadeh, 1982).
600 K
Also, the temperature at the surface is same as the particle
size is increased for a 0nal temperature of 600 K.
From the analysis of the product yield distribution, it ap-
pears that the particle shrinkage a4ects both the primary
1E-3 0.01 0.1
and the secondary reaction paths due to di4erent heat trans-
Particle Thickness (m)
fer conditions interior to the particle and to reduce volatile
residence times, respectively. On the whole, the shrink-
age of the particle favors the attainment of larger yields of
(volatiles and gases)1 (as in Fig. 11) at the expense of de-
crease in the formation of other two products (as in Figs. 12
and 13).
5.2.4. E6ect of speci8c heat capacity
Fig. 14 shows the dependence of product yields and con-
version time on speci0c heat capacity of biomass for 0nal
temperature of 900 K for R = 0:02 m. As is evident, the
speci0c heat capacity does not a4ect the yields of either the
primary or the secondary products. Conversion time also
does not depend on speci0c heat capacity indicating that en-
ergetics of secondary reactions are not important. The tem-
perature pro0le as a function of radial distance for di4erent
values of speci0c heat capacity, can be used to explain the
results obtained in Fig. 14. It is found that the temperature
pro0le is nearly same along the radial position for all the
values of speci0c heat capacities considered. Constant prod-
uct yields are predicted because the 9ow 0eld results only
from the net mass addition from solid to gas as speci0c heat
capacity is increased (refer Fig. 14).
 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012 2009

LEGEND
1.0 LEGEND 900
t =520 s
0.9 Bi=36.0
t =400 s
Bi=9.0
0.8 800 t =300 s
Bi=1.0
t =200 s
Biomass conversion (-)

0.7 Bi=0.25
t =100 s
700

Temperature (K)
0.6
0.5
600
0.4
0.3 500
0.2
0.1 400
0.0
300
0 100 200 300 400 500 600
Time (s) 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Radial distance (-)
Fig. 15. E4ect of Biot number on biomass conversion with cylin-
drical pellet as simulated using present model with shrinkage Fig. 17. Temperature pro0le as a function of radial distance with cylin-
(R = 0:02 m; T0 = 303 K; Tf = 900 K). drical pellet at various values of time as simulated using present model
with shrinkage (R = 0:02 m; T0 = 303 K; Tf = 900 K; Bi = 36:0).

1.0
1.0 600
0.9
LEGEND 0.9
0.8 500
t =100 s 0.8
Biomass concentration (-)

0.7 t =200 s 0.7

Product yields (-)

LEGEND 400

Pyrolysis time (s)

t =300 s
0.6 0.6 Pyrolysis time
t =400 s
(Volatile & Gases)1
0.5 t =541 s 0.5 (Char)1 300
0.4 (Char)2 or (Volatile & Gases)2
0.4
200
0.3
0.3
0.2
0.2 100
0.1
0.1
0.0 0
0.0
0 5 10 15 20 25 30 35
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Biot number (-)
Radial distance (-)
Fig. 18. Final product yields and pyrolysis time as functions of Biot
Fig. 16. Biomass concentration pro0le as a function of radial distance number with cylindrical pellet as simulated using present model with
with cylindrical pellet at various values of time as simulated using present shrinkage (R = 0:02 m; T0 = 303 K; Tf = 900 K).
model with shrinkage (R = 0:02 m; T0 = 303 K; Tf = 900 K; Bi = 0:25).

tion. Fig. 17 shows the temperature pro0le as a function

5.2.5. E6ect of Biot number of radial distance with t as a parameter for Bi = 36:0. It is
The conversion of biomass with respect to pyrolysis time found that the temperature gradient is nearly the same for
is shown in Fig. 15 for various values of Biot number for low value of Biot number (Bi = 0:25) also. The tempera-
R = 0:02 m. It can be seen that at any given time, there is an ture pro0le is linear after the completion of pyrolysis for
increase in biomass conversion as the Biot number increases. both the cases. The pyrolysis conversion time for Bi = 0:25
Since the Biot number is de0ned by Eq. (34), for a speci0ed is more (541 s) as compared to Bi = 36:0 (520 s), i.e., as
value of R, an increase in Biot number is accompanied by an the Biot number increases rate of completion of pyrolysis
enhancement in the rate of heat transfer, which in turn, ac- is faster. Therefore, it can be stated that the progress of py-
celerates the pyrolysis reaction. Biomass concentration pro- rolysis reaction is controlled by the heat transfer rate inside
0le as a function of radial distance for Bi = 0:25 (low value) the solid particle for small values of Biot number. However,
is shown in Fig. 16. Similar trend is observed for high value both rates including the heat transfer and the chemical re-
of Biot number (Bi = 36:0) also. It is found that the time for action are important in determining the overall rate of the
completion of pyrolysis for Bi = 36:0 is less (i.e., 520 s) as reaction when the value of Biot number is large.
compared to Bi = 0:25 (i.e., 541 s). This is due to the fact The main objective of the pyrolysis of a solid is usually
that a smaller value of Bi at any speci0ed value of R cor- to obtain product yields. Therefore, it is also important to
responds to a smaller heat transfer rate. This consequently know the e4ect of Bi on product yields in the solid particle.
gives rise to a predominantly heat-transfer-controlled reac- Fig. 18 shows the 0nal product yields and pyrolysis time as
2010 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012

functions of Biot number. There is slight decrease in pyrol- • The progress of pyrolysis reaction is controlled by heat
ysis time as Bi increases. It can be seen that Biot number transfer rate inside the solid particle for small values of
does not a4ect both primary and secondary product yields. Biot number. However, both the heat transfer rate and
As stated previously, the temperature is nearly the same at the chemical reaction rate are important in determining
any speci0ed time, t, and radial position of the particle, as Bi the overall rate of reaction for the large values of Biot
increases from 0.25 to 36.0, and hence the rate of pyrolysis number.
reaction is same. • The model is used to examine the impact of shrinkage,
to have an understanding of how it can a4ect the pyroly-
6. Conclusions sis process, and to gain knowledge on what pyrolysis or
combustion conditions must be considered. This can pro-
The impact of shrinkage on pyrolysis of biomass parti- vide an improved qualitative understanding of pyrolysis
cles is studied employing a kinetic model coupled with heat and guide further research into modeling of biomass py-
transfer model using a practically signi0cant kinetic scheme rolysis and combustion.
consisting of physically measurable parameters. The shrink- • The results discussed above have a lot of practical im-
age model has been used to examine the impact of shrink- portance and physical signi0cance in industrial pyrolysis
age on particle size, pyrolysis time, product yields, speci0c applications. The results are also important and useful for
heat capacity and Biot number. Simulations are carried out design of biomass gasi0ers, reactors, etc.
for temperatures ranging from 303 to 900 K, the particle ra-
dius ranging from 0.0000125 to 0:05 m and shrinkage fac-
Notation
tors ranging from 0.0 to 1.0. Based on the results obtained
and the discussions carried out in the earlier section, the fol- A1 ; A2 ; A3 frequency factor, s−1
lowing conclusions are drawn: b geometry factor (slab=1, cylinder=2,
sphere=3)
• The simulated results obtained from the model in the
B virgin biomass
present study with shrinkage (
= 0:2;
= 0:0; #
= 0:2)
C1 (char)1
are in excellent agreement with a wide range of ex-
C2 (char)2
perimental results reported in literature (Sha0zadeh
et al., 1979; Pyle and Zaror, 1984; Scott et al., 1988) as CB concentration of B, kg m−3
compared to the model developed by earlier researchers CG1 concentration of G1 , kg m−3
(Bamford et al., 1946; Liliedahl and SjRostrRom, 1998; CC1 concentration of C1 , kg m−3
Jalan and Srivastava, 1999; Babu and Chaurasia, 2003a). CG2 concentration of G2 , kg m−3
• The choice of lower possible values of shrinkage factor CC2 concentration of C2 , kg m−3
(
= 0:2;
= 0:0; #
= 0:2) in the present study is more Cp speci0c heat capacity, J kg−1 K −1
realistic of incorporating shrinkage e4ect, and hence re- d pore diameter, m
sulted in better model predictions, as against relatively D1 ; D2 constants de0ned by expressions of k1 and k2 ,
higher values (
= 0:5;
= 0:0; #
= 0:5) as taken by respectively, K
Di Blasi (1996a). E3 activation energy de0ned by expression of k3 ,
• The impact of shrinkage is signi0cant on the pyrolysis in J mol−1
several ways. It includes the reduction of residence time of G1 (gases and volatiles)1
gases within the particle, cooling of the char layer due to G2 (gases and volatiles)2
higher mass 9ux rates of pyrolysis products, and thinning h convective heat transfer coeJcient,
of the pyrolysis reaction region. W m−2 K −1
• The higher heat transfer rates of the shrinking particle H modi0ed Biot number
reduce the pyrolysis time. k thermal conductivity, W m−1 K −1
• Shrinkage has negligible a4ect on pyrolysis in thermally k1 ; k2 ; k3 rate constants, s−1
thin regime. However, shrinkage a4ects both the pyrolysis l axial length of cylinder, m
time and yield of pyrolysis products in thermally thick L1 ; L2 constants de0ned by expressions of k1 and k2
regime, and results in the formation of ‘thermal wave’ at respectively, K 2
the surface of the particle. M mass, kg
• The shrinkage of the particle favors the attainment of n1 ; n2 ; n3 orders of reactions
larger yields of (volatiles and gases)1 at the expense of N total number of equations used in the simulation
other two products. of the model
• Speci0c heat capacity does not a4ect the primary and Q de0ned by Eq. (35), m3 kg−1
secondary product yields. Conversion time also does not r radial distance, m
depend on speci0c heat capacity indicating that energetics R radius for cylinder and sphere; half thickness for
of secondary reactions are not important. slab, m
 B.V. Babu, A.S. Chaurasia / Chemical Engineering Science 59 (2004) 1999 – 2012 2011

Rc universal gas constant, J mol−1 reactions. Proceedings of International Symposium & 55th Annual
t time, s Session of IIChE (CHEMCON-2002), OU, Hyderabad, India,
T temperature, K pp. 105–106. (Also available via Internet as .pdf 0le at
http://bvbabu.50megs.com/custom.html/52).
V total particle volume, sum of the volume occu-
Babu, B.V., Chaurasia, A.S., 2003a. Modeling for pyrolysis of solid
pied by pores and by the solid phase, m3 particle: kinetics and heat transfer e4ects. Energy Conversion and
Vg volume occupied by the pores, i.e., by the gases Management 44, 2251–2275 (also available via Internet as .pdf 0le at
and volatiles, m3 http://bvbabu.50megs.com/custom.html/50).
VS solid-phase (wood and char) volume, m3 Babu, B.V., Chaurasia, A.S., 2003b. Modeling, simulation, and estimation
VS0 initial e4ective solid volume, m3 of optimum parameters in pyrolysis of biomass. Energy Conversion
and Management 44, 2135–2158 (also available via Internet as .pdf
x dimensionless radial distance 0le at http://bvbabu.50megs.com/custom.html/47).
X conversion of biomass Babu, B.V., Chaurasia, A.S., 2003c. Modeling & simulation of
pyrolysis of biomass: e4ect of heat of reaction. Proceedings
Greek letters of International Symposium on Process Systems Engineering
and Control (ISPSEC ’03)—for Productivity Enhancement
 thermal di4usivity, m2 s−1 Through Design and Optimization, IIT-Bombay, Mumbai, India,

shrinkage factor (de0ned by Eq. (19)) pp. 181–186. (also available via Internet as .pdf 0le at


shrinkage factor (de0ned by Eq. (20)) http://bvbabu.50megs.com/custom.html/55)

Babu, B.V., Chaurasia, A.S., 2003d. Optimization of pyrolysis of
# shrinkage factor (de0ned by Eq. (22))
biomass using di4erential evolution approach. Proceedings of the
LH heat of reaction, J kg−1 Second International Conference on Computational Intelligence,
L axial grid length Robotics, and Autonomous Systems (CIRAS-2003), Singapore,
Lx radial grid distance pp. 787–792 (also available via Internet as .pdf 0le at
 emissivity coeJcient http://bvbabu.50megs.com/custom.html/73).
Babu, B.V., Chaurasia, A.S., 2004a. Dominant design variables in


void fraction of particle as de0ned by Eq. (27),
pyrolysis of biomass particles of di4erent geometries in thermally thick
0

at initial condition regime. Chemical Engineering Science 59, 611–622.
! reaction progress variable Babu, B.V., Chaurasia, A.S., 2004b. Parametric study of thermal and
 normalized temperature thermodynamic properties on pyrolysis of biomass in thermally thick
 density, 0 at initial condition, kg m−3 regime. Energy Conversion and Management 45, 53–72 (also available
via Internet as .pdf 0le at http://bvbabu.50megs.com/custom.html/62).
 Stefan Boltzmann constant, W m−2 K −4
Babu, B.V., Chaurasia, A.S., 2004c. Pyrolysis of biomass: improved
 dimensionless time models for simultaneous kinetics and transport of heat, mass, and
momentum. Energy Conversion and Management 45, 1297–1327.
Dimensionless numbers Babu, B.V., Angira, R., Nilekar, A., 2004. Optimal design of an
auto-thermal ammonia synthesis reactor using di4erential evolution.
Bi Biot number Accepted and to be Presented at the Eighth World Multi-Conference
Pr Prandtl number on Systematics, Cybernetics and Informatics (SCI-2004), July 18–21,
Q

heat of reaction number Orlando, FL, USA.
Re Reynolds number Bamford, C.H., Crank, J., Malan, D.H., 1946. The combustion of wood.
Part I. Proceedings of the Cambridge Philosophical Society 42,
166–182.
Subscripts
Bradbury, A.G.W., Sakai, Y., Sha0zadeh, F., 1979. A kinetic model
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0 initial Bryden, K.M., Ragland, K.W., Rutland, C.J., 2002. Modeling thermally
f 0nal thick pyrolysis of wood. Biomass and Bioenergy 22, 41–53.
B wood Carnahan, B., Luther, H.A., James, O.W., 1969. Applied Numerical
C char Methods. Wiley, New York.
e4 e4ective Chan, W.R., Kelbon, M., Krieger, B.B., 1985. Modeling and experimental
veri0cation of physical and chemical processes during pyrolysis of
m mean large biomass particle. Fuel 64, 1505–1513.
Chan, W.R., Kelbon, M., Krieger-Brockett, B., 1988. Single-particle
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