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Effect of endothermic reaction mechanisms on the coupled heat and

mass transfers in a porous packed bed with Soret and Dufour effects
Mingchun Li

, Yusheng Wu, Zhongliang Zhao


School of Material Science and Engineering, Shenyang University of Technology, Shenyang 110023, China
a r t i c l e i n f o
Article history:
Received 9 November 2011
Received in revised form 3 April 2013
Accepted 3 August 2013
Available online 4 September 2013
Keywords:
Porous packed bed
Heat and mass transfer
Reaction mechanisms
Cross-diffusion effects
Non-thermal equilibrium
a b s t r a c t
Taking the inuences of chemical reaction mechanisms into account, a mathematical model has been
developed to simulate the coupled heat and mass transfer as well as endothermic reactions in a non-ther-
mal equilibrium packed bed with Soret and Dufour effects, which was numerically solved and validated
by comparing with experimental data. It was found that the chemical reaction mechanisms have a great
inuence on the calculated solutions, and the cross-diffusion effects on the reactive characteristics of the
packed beds are diverse under different chemical reaction mechanism. For the heat transfer controlled
mechanism, the maximum reductions of the concentration of gas product and the solid fractional conver-
sion induced by the Soret and Dufour effects are 25.1% and 14.4% respectively at supercial velocity
53.3 cm s
1
and the Nusselt number 4.1. However for the mass transfer controlled model, the calculated
solid fractional conversions are higher than that obtained by neglecting the cross-diffusion effects and the
increase being less than 16% at supercial velocity 11.9 cm s
1
and the Sherwood number 47.1. The dif-
ferences induced by the Soret and Dufour effects are demonstrated numerically to increase gradually
with the Nusselt number or the Sherwood number.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Heat and mass transfer with chemical reactions in porous
packed beds is of considerable importance in chemical and metal-
lurgical industries, such as hydrodesulfurization multiphase
reactors, ue gas denitrication reactors, enzymatic acidolysis
reactors, catalytic conversion reactors, ore calcinations furnaces,
etc. The reaction conversion processes are mainly inuenced by
diffusion and convection, and in turn the heat and mass transfer
can be altered tremendously by chemical reactions. Depending
on the chemical reaction occurs whether at a phase interface or
as a single phase volume reaction, which can be classied as heter-
ogeneous and homogeneous processes. In general, most researches
related the heat and mass transfer in porous media with chemical
reactions focus on the transport processes within catalytic porous
media or the rst-order reaction systems [1,2]. Chao et al. [3]
investigated the heat and mass transfer of chemically-reactive
steady stagnation ows in catalytic porous beds according to
Arrhenius kinetics and Singular perturbation analysis. Ulson De
Souza et al. [4] used a two scale model to study the mass transfer
in a packed bed with a heterogeneous chemical reaction by taking
into account dispersion in the main uid phase, internal diffusion
of the reactant in the pores of the catalyst, and surface reaction
inside the catalyst. They employed volume averaging and Darcys
law for a spatially periodic porous medium. Beg et al. [5] examined
the steady double-diffusive free convective heat and mass transfer
of a chemically-reacting micropolar uid owing through a Dar-
cian porous regime adjacent to a vertical stretching plane. A sim-
plied rst order homogenous reaction model was used to
simulate the chemical reaction in the ow. In their analysis, Chem-
ical reaction was shown to decelerate the ow and also micro-rota-
tion values, in particular near the wall. Alam et al. [6] investigated
the effects of thermophoresis and the homogeneous rst order
chemical reactions on magneto-hydrodynamic mixed convective
ow past a heated inclined permeable at plate in the presence
of heat generation or absorption. Zueco et al. [7] investigated the
free convection boundary layer ow and heat and mass transfer
across an isothermal cylinder embedded in an isotropic, homoge-
nous, saturated porous regime also with a rst-order chemical
reaction in the diffusing species. An exponent-function kinetic
model was constructed in their work for the simulation of the cat-
alytic coupling reaction. The effect of rst order chemical reaction
and thermal radiation on hydromagnetic free convection heat and
mass transfer ow of a micropolar uid via a porous medium
bounded by a semi-innite porous plate with constant heat source
in a rotating frame of reference was studied by Das et al. [8].
Most of the above studies only considered the rate of the
chemical reaction itself based on the micro-kinetics using simple
reaction model. However, it is known that the actual chemical
0017-9310/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijheatmasstransfer.2013.08.004

Corresponding author. Tel.: +86 13604187687.


E-mail address: liming-799@163.com (M. Li).
International Journal of Heat and Mass Transfer 67 (2013) 164172
Contents lists available at ScienceDirect
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reactions in packed beds are accompanied by the heat and mass
transfer processes through gas lm and solid product layers in
addition to pure chemical reaction [9]. To predict accurately the
ow behavior and reaction rate, it is necessary to take macro-
kinetics reaction mechanisms into account. The analysis of the heat
and mass transfer in porous media becomes complicated when
multiphase chemical reactions related to heat and (or) mass
exchanges between the owing uid and the porous solid matrix.
Maikov and Director [10] studied the mass transfer processes in
polydisperse porous media and investigated the kinetic regime of
methane pyrolysis in a porous carbon skeleton considering
external and internal diffusion resistances for different initial
distributions of particles forming the porous medium. Valipour
[11] presented a mathematical model to simulate the multiple
heterogeneous reactions with complex set of physicochemical
and thermal phenomena in a moving bed of porous pellets. Daggu-
pati [12] examined a solid conversion process during hydrolysis
and decomposition of cupric chloride in a uidized bed reactor,
in which the reaction rate was determined by shrinking-core
model. Sahir [13] presented the kinetics of copper oxidation in
the air reactor of achemical looping combustion system using the
law of additive reaction times, which took into account the pore
diffusion of gaseous species in the interior of the porous oxygen
carrier but only appropriate when pore diffusion is controlling.
Although these studies take the multiphase chemical reactions
and the transfer processes together into account, but no consider-
ation about the cross-diffusion effects and no discussions on the
inuences of chemical reaction mechanisms were given in these
studies.
The roasting, reduction and decomposition of ores are the
important kinds of endothermic gassolid reactions employed
extensively in metallurgy and chemical industries [14]. These ther-
mal decomposition reactions with gaseous and solid products are
quite complex reactions inuenced by many factors, including
the chemical reaction itself, diffusion transport on different scales
in the porous solid, external mass transfer, heat transfer, etc. So the
cross-coupled effects among the heat and mass transfer as well as
the endothermic reactions must be considered as the temperature
gradient and the concentration gradient exist simultaneously.
The energy ux caused by a composition gradient is termed the
Dufour or diffusion-thermo effect. On the other hand, mass ux can
also be created by temperature gradients and this embodies the
Soret or thermal-diffusion effect. Ecket and Drake [15] presented
several cases that the Dufour effect cant be neglected. A primary
discussion on the effect of the cross-coupled diffusion in a system
with horizontal temperature and concentration gradients was
made by Malashetty et al. [16]. Benano-Melly et al. [17] analyzed
the heat diffusion of a binary uid mixture in a porous medium
with a horizontal thermal gradient. Adrian Postelnicu [18] ana-
lyzed numerically the heat and mass transfer characteristics of nat-
ural convection about a vertical surface embedded in a saturated
porous medium subjected to a chemical reaction, by taking into ac-
count the Dufour and Soret effects. Mansour et al. [19] investigated
the effects of chemical reaction, thermal stratication, Soret num-
ber and Dufour number on MHD free convective heat and mass
transfer of a viscous, incompressible and electrically conducting
uid on a vertical stretching surface embedded in a saturated por-
ous medium. Ibrahim et al. [20] discussed the effect of chemical
Nomenclature
a, b, c stoichiometric coefcients
c
1
, c
2
mass fraction of species C and inertial gas in the main
owing gas
C
0
, C
0
concentration of species C at the surface of solid pellets
and the equilibrium concentration (kg m
3
)
C
p,1
, C
p,d
specic heat of species C and inertial gas (kJ mol
1
K
1
)
d particle diameter (m)
D, D
se
effective diffusivities of gas product in packed bed and
solid product layer (m
2
s
1
)
D
0
, D
00
thermal diffusion coefcient and the Dufour coefcient
(m
2
s
1
K
1
)
f
s
solid fractional conversion
G
A
moles of reactant A (mol)
h
d
interfacial mass transfer coefcient (m s
1
)
h
f
interfacial heat transfer coefcient (W m
2
K
1
)
DH enthalpy of dissociation (kJ mol
1
)
k
f
uid conductivity (W m
1
K
1
)
L reactor length (m)
L
1q
, L
q1
cross-diffusion coefcients (kg K m
1
s
1
)
M
1
, M
2
, M
s
molecular mass of species C, inertial gas and solid
reactant (g mol
1
)
Nu the Nusselt number
N
c
diffusion rate of species C across solid product layer and
gas lm (kg s
1
)
Pe the Peclet number
P
CO2
equilibrium dissociation pressure (Mpa)
q
c
heat transfer rate (W)
q
w
dimensionless constant heat ux at the wall
r coordinate variable in radial direction (m)
r
c
un-reacted core radius (m)
r
in
initial pellet radius (m)
r
s
radius of limestone pellets (m)
Pe dimensionless radial coordinate, r/R
R cylindrical reactor diameter (m)
R
A
overall reaction rate of a single particle (mol s
1
)
R
gas
the gas constant (J K
1
mol
1
)
R
i
REV
overall reaction rate on the scale of REV (mol s
1
)
i superscript indicates the reaction mechanism, i = 1 ,2
S
REV
surface area of REV (m
2
)
Sh the Sherwood number
t time (s)

t dimensionless time scale,



t tD=L
2
T temperature of environment (K)
T
b
, T
c
, T
s
temperatures of the owing gas, the unburnt core and
the surface of solid pellets (K)
T
in
initial thermal gas temperature (K)
Th the Thiele number
T; T
c
; T
s
dimensionless temperatures of the owing gas, the un-
burnt core and the surface of solid pellets
v effective velocity of owing gas in porous media (m s
1
)
v
b
supercial velocity of uid (m s
1
)
V
REV
volume of REV (m
3
)
x longitudinal coordinate (m)
x dimensionless axial length scale, x/L
Greek symbols
e porosity
e
p
porosity of limestone pellets
k
e
effective thermal conductivity of the solid product
(W m
1
K
1
)
l dynamic viscosity (kg s
1
m
1
)
q density of the mixture gas (kg m
3
)
q
s
density of the solid reactant (kg m
3
)
q
p
density of limestone pellets (kg m
3
)
M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172 165
reaction on free convection heat and mass transfer for a non-New-
tonian power law uid over a vertical at plate embedded in a
uid-saturated porous medium in the presence of the yield stress
and the Soret effect.
Literature review shows that no study on the inuences of ki-
netic reaction mechanisms in a non-thermal equilibrium porous
packed bed with endothermic reaction, forced convection and the
cross-diffusion effects were reported so far. In the present paper,
the coupled heat and mass transfer in a non-thermal equilibrium
packed bed considering Soret and Dufour effects are studied under
different macro-kinetics reaction mechanisms, in accordance with
the dictates of thermodynamics of irreversible processes, reaction
engineering principles and the local thermal non-equilibrium
model.
2. Modeling and formulation
2.1. Problem description
A cylindrical reactor lled with spherical specimens subjects to
a constant heat ux boundary condition as shown in Fig. 1(a). The
diameter of the packed bed is 2R, and the length of which is L.
The solid sphere particles are of uniform shape and undeformable.
The high temperature feeding gas ows through the bed by forced
convective and exchanges heat with the solid matrix. The endo-
thermic decomposition reactions take place as the particle temper-
ature rises. The gas product diffuses from the reactive interface
into the main stream under the co-acting of the pressure difference
and the temperature difference. Here, the natural convection and
the radiation heat transfer are neglected, and the owing gas is as-
sumed to be incompressible.
2.2. Reaction kinetics
The present model describes the kinetic and thermal behavior
of solid pellets in packed bed, in which a heterogeneous endother-
mic reaction of the type given by Eq. (1) takes place.
aAsolid
heating
bBsolid cCgas 1
The overall processes contain essentially heat and mass transport
steps and chemical reaction at interface as is schematically shown
inFig. 1(b), whichcanbe summarizedas the following several stages:
(1) Heat transfer fromenvironment to the surface of solidparticle. (2)
Heat transfer from the particles external surface to the reaction
interface, the process of the heat conductivity through the solid
product layer is assumed a pseudo-steady state. (3) Endothermic
decompositionreactionbegins at the reactioninterface, andthe tem-
perature of the unreacted core remained constant. (4) Gas product C
diffuses through the porous solid layer, which extends fromthe reac-
tion interface to the particles exterior. (5) Diffusion of gas product C
fromparticles exterior surface to the environment. Appearance of an
overall decomposition process substantially changes with different
contributions of each elemental step.
2.2.1. Heat transfer controlled scheme
Consider a spherical sample of radius r
in
and at an initial
temperature T
c
, be suspended in a large furnace maintained at a
temperature T
b
. Based on the additive theory of the transfer
resistances, the amount of heat that reaches the reactive interface
from environment of the pellet is given by [21]
q
c
4pr
2
in
T
b
T
c
h
f
=1 h
f
r
in
=k
e
r
in
=r
c
1 2
Dening the modied Nusselt number Nu h
f
r
in
=k
e
.
Assuming the entire amount of heat transferred from the envi-
ronment to the sample was used up for the endothermic reac-
tion(q
c
= R
A
DH), and the initial temperature of gas product is the
same to the interface temperature. Then the overall reaction rate
of a single pellet R
A
in heat transfer controlled regime (i = 1) can
be given as follows
R
A
4pr
2
in
T
b
T
c
h
f
= 1 h
f
r
in
=k
e
r
in
=r
c
1DH f g 3
In a packed bed, the minimal unit is the representative elemen-
tary volume (REV). The surface area of REV can be written as
follows
S
REV
V
REV
31 e=r
in
4
According to Eqs. (3) and (4), the overall reaction rate of REV in heat
transfer controlled regime (i = 1) can be derived as:
R
1
REV
V
REV
31 e=r
in
T
b
T
c
h
f
= 1 h
f
r
in
=k
e
r
in
=r
c
1DH f g 5
The quantity R
1
REV
denotes the production mole of the gas product C
per unit time in REV, which equals to the exhaustive mole of reac-
tant A per unit time in REV (c/a) dG
A
/dt, that is
V
REV
31 e=r
in
T
b
T
c
h
f
1 h
f
r
in
=k
e
r
in
=r
c
1DH

c
a
V
REV
1 e
4pr
3
in
=3
4pr
2
c
q
s

M
s
dr
c
dt
6
Separating the variables in Eq. (6) and integrating gives the position
of the calcination front r
c
as a function of time and the surrounding
temperature.
ah
f
M
s
=cr
in
DHq
s

_
t
0
T
b
T
c
dt
1 h
f
r
in
=k
e
1 r
c
=r
in

3
=3 h
f
r
in
=k
e
1r
c
=r
in

2
=2 7
Fig. 1. The packed bed with endothermic reaction and the decomposition scheme for a single spherical specimen.
166 M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172
Noting that f
s
1 r
3
c
=r
3
in
, where f
s
is the solid fractional conversion
of REV at time t, Eq. (7) may be restated as follows
ah
f
M
s
=cr
in
DHq
s

_
t
0
T
b
T
c
dt
1 h
f
r
in
=k
e
f
s
=3 h
f
r
in
=k
e
1 1 f
s

2=3
=2 8
2.2.2. Mass transfer controlled scheme
On the basis of pseudo-steady state assumption, the rate of dif-
fusion of the gas product C away from the decomposition interface
may be given by [21]
N
C
4pD
se
C
0
C
0
r
in
r
c
=r
in
r
c
9
The diffusion rate of gas product C from particles exterior surface to
environment is given by
N
C
4pr
2
in
h
d
C
0
qc
1
10
Eqs. (9) and (10) may be solved for C
0
C
0
D
se
C
0
r
in
r
c
=r
in
r
c
r
2
in
h
d
qc
1
=r
2
in
h
d
D
se
r
in
r
c
=r
in
r
c

11
Substituting the value of C
0
in Eq. (10) and rearranging, the overall
reaction rate of a single pellet R
A
in mass transfer controlled regime
can be given as follows
R
A
4pr
2
in
h
d
C
0
qc
1
=1 h
d
r
in
=D
se
r
in
=r
c
1 12
Dening the modied Sherwood number Sh = (h
d
r
in
/D
se
). Hence the
overall reaction rate of REV in mass transfer controlled regime
(i = 2) can be given by
R
2
REV
V
REV
31 e=r
in
h
d
C
0
qc
1
=1 h
d
r
in
=D
se
r
in
=r
c
1
13
Similar to the derivation of Eq. (7), the position of the calcination
front r
c
in mass transfer controlled regime as a function of time
and the surrounding concentration are obtained as follows
aM
s
=cq
s

_
t
0
C
0
qc
1
dt r
in
1r
c
=r
in

3
=3h
d
r
2
in
=D
se
f1
r
c
=r
in

2
=21r
c
=r
in

3
=3g 14
2.3. Conservation equations
The model is two-dimensional and transient. The variables and
parameters are therefore functions of the axial position in the
packed bed x, the radial position in the packed bed r and time t.
Throughout what follows, the variables v(r), c
1
(x, r, t), T
b
(x, r, t),
T
s
(x, r, t), r
c
(x, r, t) and f
s
(x, r, t) will be termed principal variables,
and are calculated respectively from the above reaction kinetics
models and the conservation equations given below.
The mass balance for gas product C considering the cross diffu-
sion effects on the scale of REV is given by
eq
@c
1
@t
eq
1
r
@
@r
rD
@c
1
@r
_ _
e
@
@x
qc
1
c
2
D
0
gradT qDgradc
1

eqm
@c
1
@x
R
i
REV
=V
REV
15
The energy conservation equation of the main stream consider-
ing the cross diffusion effects is given by
eq
@1 c
1
C
p;d
c
1
C
p;1
T
b
@t
e
1
r
@
@r
rk
f
@T
b
@r
_ _
e
@
@x
k
f
gradT
b
qc
1
l
c
11
T
b
D
00
gradc
1

emq
@1 c
1
C
p;d
c
1
C
p;1
T
b
@x
S
v
h
f
T
b
T
s

R
i
REV
=V
REV
C
P;1
T
b
T
c
; 16
R
i
REV
=V
REV

31e=r
in
T
b
T
c
h
f
=f1h
f
r
in
=k
e
r
in
=r
c
1DHg; i 1
31e=r
in
h
d
C
0
qc
1
=1h
d
r
in
=D
se
r
in
=r
c
1; i 2
_
17
The effective velocity v may be determined from the supercial
velocity v
b
and the porosity of packed beds v = v
b
/e, and the Ergun
ForchheimerBrinkman equation [22] is used for analyzing the
uid ow in the porous packed bed,

dP
dx
150
lm
b
d
2
1 e
2
e
3
1:75
q
f
m
2
b
d
1 e
e
3

l
e
1
r
d
dr
r
dm
b
dr
_ _
18
The surface temperature of the solid pellets T
s
as a function of
surrounding temperature T
b
and the calcination front r
c
is given
by the following relationship which takes into account the heat
transfer resistances of both the external lm and the solid product
layer [22].
T
s
h
f
r
in
=k
e
T
b
r
c
T
c
=r
in
r
c
=h
f
r
in
=k
e
r
c
=r
in
r
c
19
The function of the calcination front r
c
included in Eqs. (15),
(16), (17), and (19) depend on the reaction kinetics model chosen.
The expression of Eq. (7) is used in the heat transfer controlled
model, while that of Eq. (14) is used in the mass transfer controlled
model.
The following dimensionless variables are introduced for nor-
malizing the governing equations

t tD=L
2
; x x=L; r r=R; T T
b
=T
in
; T
c
T
c
=T
in
; T
s
T
s
=T
in
20
Utilizing Eq. (20), the dimensionless governing balance equation of
Eqs. (15)(17) can be rewritten as:
@c
1
@

t

L
2
R
2
r
@
@r
r
@c
1
@r
_ _

@
2
c
1
@x
2

D
0
T
in
D
@
@x
c
1
c
2
@T
@x
_ _
m
L
D
@c
1
@x
R
i
REV
=V
REV
_ _
21
Fig. 2. Comparison of the calculated results under different chemical reaction
mechanisms with the experimental data in literature [14]. (T
c
= 1073 K; e
p
= 0.09;
q
p
= 2.47 10
3
kg m
3
; v
b
= 1.32 cm s
1
; e = 0.47) calculated results, D
0
= D
00
= 0,
i = 1; calculated results, D
0
= D
00
= 0, i = 2; s calculated results,
D
0
= D
00
= 0.0008 cm
2
s
1
K
1
, i = 1; r calculated results, D
0
= D
00
= 0.0008 cm
2
s
1
-
K
1
, i = 2.
M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172 167
@1 C
p;1
=C
p;d
1c
1
T
@

t

L
2
R
2
1
qC
p;d
D
1
r
@
@r
rk
f
@T
@r
_ _

k
f
qC
p;d
D
@
2
T
@x
2

D
00
DC
p;d
@
@x
c
1
l
c
11
T
@c
1
@x

Lm
D
@1 C
p;1
=C
p;d
1c
1
T
@x

L
2
DeqC
p;d
S
v
h
f
T T
s

R
i
REV
=V
REV
C
P;1
T T
c

C
p;d
22
Let Pe = vL/D, Th=R
(i)
REV
L
2
/(Deq), Pe is the modied Peclet number
which represents the relative convection velocity and diffusion
velocity, Th is the Thiele modulus that reects the relative endo-
thermic chemical reaction rate and diffusion velocity.
The initial and boundary conditions for the problem are:
c
1
x; r; 0 0; Tx; r; 0 T
c
; r
c
x; r; 0 r
in
; c
1
0; r;

t 0;
T0; r;

t 1; @c
1
x; 0;

t=@r 0; @Tx; 0;

t=@r 0;
@c
1
1; r;

t=@x 0; @T1; r;

t=@x 0; @c
1
x; 1;

t=@r 0;
@Tx; 1;

t=@r

q
w
2.4. Expression of parameters
The specic heats, density and the enthalpy of reaction are
known for a given reaction and constituents. This work takes the
limestone decomposition as an example for computation. The
other parameters are determined as follows.
The heat transfer coefcient h
f
and mass transfer coefcient h
d
through the stagnant gas lm are calculated from the following
equations [23],
h
f
k
f
2:0 1:1C
p;1
l=k
f

1=3
qmd=l
0:6
=d;
h
d
D2:0 0:6lq=D
1=3
qmd=l
1=2
=d 24
The Soret and Dufour coefcients are expressed by [24]
D
0
L
1q
=qc
1
c
2
T
2
; D
00
L
q1
=qc
1
c
2
T
2
25
the Dufour coefcient is equal to the Soret coefcient in value for
the same research system by the Onsagers reciprocity relation
L
1q
= L
q1
, and the value of which is 0.0008 cm
2
s
1
K
1
in this work
corresponding to the conditions of the owing gas in the xed bed
of limestone calcinations at 1373 K.
l
c
11
R
gas
TM
1
=fc
1
M
1
c
1
M
1
M
2
g 26
In the present work, the equilibrium concentration C
0
is calcu-
lated from the equilibrium dissociation pressure of gaseous prod-
uct (carbon dioxide) over the solid pellets as follows [25]
log p
CO
2
8792:3=T 10:4; C
0
p
CO
2
=R
gas
T 27
3. Results and discussion
The ADI (alternate dimension implicit) method [26,27] was
used to solve numerically the two-dimensional mathematical
model established in previous sections. Computations have been
carried out for a half of the cylindrical packed bed (L R). The re-
sults are independent of the time step size Dt = 0.01 s and the
number of grids 50 40. L = 0.18 m, R = 0.045 m, r
in
= 0.004 m.
3.1. Model validation
A comparison is made among the results of the experimental
data in literature [14] and the two groups of numerical solutions
obtained by the established mathematical model under different
chemical reaction mechanisms as shown in Fig. 2. It can be seen
in Fig. 2 that the chemical reaction mechanisms have a great inu-
ence on the simulated solutions. The results calculated by the heat
transfer controlled regime are in good agreement with the experi-
mental data, especially at the initial and middle stages of the
decomposition, the maximum relative error being less than
13.5%. But as the solid fractional conversion exceeds 80%, the max-
imum relative error between the simulation results and experi-
mental data increases to 23.6%. In contrast, the simulation results
under mass transfer control mechanism are much higher than
the experimental results at the initial and middle stages of the
thermal decomposition and the maximum relative error reaches
43.4%, while in good agreement with the experimental results at
the latter stage (f
s
> 80%) with the maximum relative error being
less than 12.1%. This shows that with the continuously thickening
0.0 0.2 0.4 0.6 0.8 1.0
0.00
0.05
0.10
0.15
D'=D''=0
---- D'=0, D''=0.0008 cm
2
.s
-1
.K
-1 f
s
x/L
1- v
b
=18.7 cm.s
-1
2- v
b
=37.9 cm.s
-1
3- v
b
=53.3 cm.s
-1
3
2
1
(b). Solid fractional conversion along axial direction
Fig. 3. Inuences of the supercial velocity on the concentration gradient and the Dufour effect. (i = 1; T
c
= 1170 K; T
in
= 1373 K; e = 0.42; t = 120 s; Nu = 1.9; r 0).
R
i
REV
=V
REV

31 e=r
in
L
2
h
f
T
in
T T
c
=fDeq1 h
f
r
in
=k
e
r
in
=r
c
1DHg; i 1
31 e=r
in
L
2
h
d
qc
1
C
0
=fDeq1 h
d
r
in
=D
se
r
in
=r
c
1g; i 2
_
23
168 M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172
of the solid product layer, the controlling step of reaction rate is
also continually changing. For the heat transfer controlled model
(i = 1), the solid fractional conversions calculated considering the
cross-diffusion effects are lower than those obtained by neglecting
the cross-diffusion effects and the decrease being less than 10%.
However for the mass transfer controlled model (i = 2), the solid
fractional conversions calculated considering the cross-diffusion
effects are higher than that obtained by neglecting the cross-diffu-
sion effects and the increase being less than 12.6%. Hence, it is nec-
essary to discuss and identify the specic chemical reaction
mechanism for an endothermic or exothermic reaction system
with gas product during the researches of the cross-diffusion
effects.
3.2. Discussion with heat transfer controlled scheme
The temperature of the owing gas in the pores of packed beds
is a key factor affecting the endothermic reaction rate under heat
transfer control mechanism (i = 1). The Dufour coefcient D
00
de-
notes the heat transfer resulting from concentration gradient,
which affects chiey the temperature distribution and chemical
reaction rate as i = 1. Fig. 3 shows the variation of the concentration
of gas product andthe solid fractional conversion with the super-
cial velocity v
b
. As seen from Fig. 3, for heat transfer control mech-
anism, the concentration gradient of the gas product increases
with the supercial velocity and the decrease in the solid fractional
conversion caused by the Dufour effect intense accordingly. The
maximum relative error of the solid fractional conversion increases
from 4.7% to 11.1% as the supercial velocity increases from 18.7 to
53.3 cm s
1
.
Fig. 4 shows the variation of the temperature elds of the ow-
ing gas and the solid matrix, the concentration distribution of the
gas product and the conversion ratio of the solid pellets with the
Nusselt number and the cross-diffusion coefcients. From
Fig. 4(a)(c) we can see that, as the Nusselt number increases,
the temperature eld of the owing gas decreases, while the con-
centration distribution of gas product and the surface temperature
eld of the solid pellets increase. This is expected since a higher
Nusselt number can improve the quantity of heat exchange be-
tween the owing gas and the solid matrix, which results in the de-
crease in the temperature of the owing gas and the increase in the
decomposition rate near the entrance correspondingly. It was also
found that the solid conversion degree increases near the entrance
as the Nusslet number increases. But with the region where the
decomposition reaction takes place deepens down to the exit, an
increase in the Nusslet number results in an opposite effect for
the solid conversion degree (see Fig. 4(d)). Fig. 5 portrays the vari-
ations of the ratio of Th/Pe with spatial coordinate under different
Nusselt number, which means that relative to the ability of heat
Fig. 4. Inuences of the Soret and Dufour effects on the temperature elds for both the owing gas and the solid matrix, the concentration distribution of the product gas and
the solid fractional conversion at different Nusselt number. (i = 1; T
c
= 1170 K; T
in
= 1373 K; e = 0.42; t = 120 s; v
b
= 53.3 cm s
1
; r 0).
Fig. 5. Inuence of the Nusselt number on the ratio of Th/Pe in the packed bed.
(i = 1; T
c
= 1170 K; T
in
= 1373 K; e = 0.42; t = 120 s; v
b
= 53.3 cm s
1
; r 0).
M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172 169
and mass transfer, the ability of endothermic chemical reaction in-
creases in the upstream of the packed bed, whereas decreases in
the downstream as the Nusselt number increases. The overall reac-
tion rate is determined by the product of the effective heat transfer
coefcient and the temperature difference between the two
phases. Hence, the inuences of the Nusselt number on the endo-
thermic reaction rate are diverse at different spatial coordinate.
The effect of the Nusslet number on the cross-diffusion effects is
also shown in Fig. 4. A higher Nusselt number results in a larger
difference between the two groups of results calculated separately
at D
0
= D
00
= 0 and D
0
= D
00
= 0.0008 cm
2
s
1
K
1
. As the Nusselt num-
ber increases from 0.93 to 4.1, the temperature gradient of the bulk
stream and the concentration gradient of the gas product in the
packed bed both increase, which improve the Soret and Dufour ef-
fects. As a result, the maximum relative error of the concentration
of the gas product increases from 3.2% to 25.1% and that of the so-
lid fractional conversion increases from 2.6% to 14.4%. Because the
positive thermal diffusion coefcient implies the mass transfer
resulting from higher temperature to lower temperature, the
existing temperature gradient (see Fig. 4(a)) in the endothermic
Fig. 6. Inuences of the supercial velocity on the temperature gradient and the Soret effect. (i = 2; T
c
= 1170 K; T
in
= 1373 K; e = 0.42; t = 120 s; Sh = 23.5; r 0).
Fig. 7. Inuences of the Soret and Dufour effects on the temperature elds of owing gas, the concentration distribution of gas product and the solid fractional conversion at
different Sherwood number.(i = 2; T
c
= 1170 K; T
in
= 1373 K; e = 0.42; t = 120 s; v
b
= 11.9 cm s
1
; r 0).
170 M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172
reaction packed bed improves the transmission speed of the gas
product to downstream which results in the decrease of the con-
centration elds (see Fig. 4(b)). The positive Dufour coefcient D
00
means the heat transfer resulting from higher concentration to
lower concentration. As the Dufour effect is taken into account,
the heat transmission rate is reduced, which leads to the lower
temperatures for both the owing gas in the pore and the solid ma-
trix as well as a lower endothermic reaction rate (see Fig. 4(d)).
3.3. Results with mass transfer controlled scheme
For the mass transfer controlled scheme (i = 2), the concentra-
tion of gas product in the bulk ow is a key factor affecting the
endothermic reaction rate. The Soret coefcient D
0
denotes the
mass transfer resulting from temperature gradient, which chiey
affects the concentration distribution and the reaction rate. Fig. 6
shows the variation of the temperature gradient and the solid frac-
tional conversion with the supercial velocity v
b
. As seen from
Fig. 6, the temperature gradient of the owing gas decreases with
the supercial velocity and the increase in the solid fractional con-
version induced by the Soret effect decreases accordingly. The
maximum relative error of the solid fractional conversion increases
from 2.7% to 13.7% as the supercial velocity decreases from 47.4
to 11.9 cm s
1
.
The inuences of Soret and Dufour effects on the reaction char-
acteristics, the heat and mass transfer in the packed bed at differ-
ent Sherwood number are compared in Fig. 7. As seen from Fig. 7
(a) and (b), the concentration of gas product and the temperature
of the owing gas both decrease due to the additional mass and
heat transfer caused by cross-diffusion effects. Hence, the solid
conversion fraction calculated considering the cross-diffusion ef-
fects are higher than that obtained by neglecting the cross-diffu-
sion effects as i = 2 (see Fig. 7 (c)). From the comparison of the
solid curves (D
0
= D
00
= 0) and the dashed lines (D
0
= D
00
=
0.0008 cm
2
s
1
K
1
) at different Sherwood number in Fig. 7, the
authors nd that the higher Sherwood number is, the larger effects
of the Soret and Dufour coefcients are. Under the mass transfer
controlled mechanism, a high Sherwood number results in a high
decomposition rate meaning the increases in both the thermal gra-
dient of owing gas and the concentration gradient of gas product.
As a result, the Soret and Dufour effects are intensied. The maxi-
mum relative error of the concentration of gas product increases
from 7.2% to 17.7% and that of the solid fractional conversion in-
creases from 6.5% to 15.8%, as the Sherwood number increases
from 11.8 to 47.1.
4. Conclusion
Through the chemical reaction kinetics, the thermodynamics of
irreversible processes and the assumption of local thermal non-
equilibrium, a two dimensional mathematical model describing
the coupling among the heat transfer, the mass transfer and the
endothermic reaction in a non-thermal equilibrium packed bed
was established and solved. The inuences of the Soret and Dufour
effects under different chemical reaction mechanisms were
discussed.
The inuence of the cross-diffusion effects on the reactive char-
acteristics of packed beds is diverse at different chemical reaction
mechanisms. The solid fractional conversion calculated consider-
ing the cross-diffusion effects are higher than that obtained by
neglecting the cross-diffusion effects under mass transfer con-
trolled mechanism. While the cross-diffusion effects results in an
opposite effect for the solid fractional conversion under heat trans-
fer controlled mechanism. The weakened heat transfer and the
intensied mass transfer caused by the Soret and Dufour effects
lead to a decrease in the temperature of the owing gas and a
reduction in the concentration of gas product. The differences be-
tween the results including the temperature elds, the concentra-
tion of gas product and the solid fractional conversion calculated
separately at D
0
= D
00
= 0, D
0
= D
00
= 0.0008 cm
2
s
1
K
1
, are all inten-
sied by the increase either in the Nusselt number or in the Sher-
wood number. Whatever the chemical reaction mechanism, the
ignored Soret and Dufour effects willcause much error for the
endothermic reaction packed bed with high reaction rate.
Acknowledgments
This work was nancially supported by the National Natural
Science Foundation of China (51004071), the Special Project for
High-end CNC machine tools and basic manufacturing equipment
of China (2012ZX04007-021) and Liaoning Province College Excel-
lent Young Talents Fund Project (LJQ2013012).
References
[1] J.W. Veldsink, R.M.J. van Damme, G.F. Versteeg, W.P.M. van Swaaij, The use of
the dusty-gas model for the description of mass transport with chemical
reaction in porous media, Chem. Eng. J. 57 (1995) 115125.
[2] D.N. Jaguste, S.K. Bhatia, Simulation of reaction and transport in catalyst
particles with partial external and internal wetting, Int. J. Heat Mass Transfer
38 (1995) 14431455.
[3] B.H. Chao, H. Wang, P. Cheng, Stagnation point ow of a chemically reactive
uid in a catalytic porous bed, Int. J. Heat Mass Transfer 39 (1996) 30033019.
[4] S.M.A.G. Ulson De Souza, S. Whitaker, Mass transfer in porous media with
heterogeneous chemical reaction, Braz. J. Chem. Eng. 20 (2003) 191199.
[5] O.A. Beg, R. Bhargava, S. Rawat, H.S. Takhar, T.A. Beg, A study of steady
buoyancy-driven dissipative micropolar free convection heat and mass
transfer in a Darcian porous regime with chemical reaction, Nonlinear Anal.
Model. Control 12 (2007) 157180.
[6] M.S. Alam, M.M. Rahman, M.A. Sattar, Effects of chemical reaction and
thermophoresis on magneto-hydrodynamic mixed convective heat and mass
transfer ow along an inclined plate in the presence of heat generation and
(or) absorption with viscous dissipation and Joule heating, Can. J. Phys. 86
(2008) 10571066.
[7] J. Zueco, O.A. Bg, T.A. Bg, H.S. Takhar, Numerical study of chemically reactive
buoyancy-driven heat and mass transfer across a horizontal cylinder in a high-
porosity non-Darcian regime, J. Porous Med. 12 (2009) 519535.
[8] K. Das, Effect of chemical reaction and thermal radiation on heat and mass
transfer ow of MHD micropolar uid in a rotating frame of reference, Int. J.
Heat Mass Transfer 54 (2011) 35053513.
[9] S. Homma, S. Ogata, J. Koga, S. Matsumoto, Gassolid reaction model for a
shrinking spherical particle with unreacted shrinking core, Chem. Eng. Sci. 60
(2005) 49714980.
[10] I.L. Maikov, L.B. Director, Mathematical simulation of mass transfer processes
under heterogeneous reactions in polydisperse porous media, Chem. Eng. Sci.
62 (2007) 13881394.
[11] M.S. Valipour, Y. Saboohi, Modeling of multiple noncatalytic gassolid
reactions in a moving bed of porous pellets based on nite volume method,
Heat Mass Transfer 43 (2007) 881894.
[12] V.N. Daggupati, G.F. Naterer, K.S. Gabriel, Diffusion of gaseous products
through a particle surface layer in a uidized bed reactor, Int. J. Heat Mass
Transfer 53 (2010) 24492458.
[13] A.H. Sahir, J.S. Lighty, H.Y. Sohn, Kinetics of copper oxidation in the air reactor
of a chemical looping combustion system using the law of additive reaction
times, Ind. Eng. Chem. Res. 50 (2011) 1333013339.
[14] E.T. Turkdogan, R.G. Olsson, H.A. Wriedt, L.S. Darken, Calcination of limestone,
Trans. Soc. Min. Eng. AIME 254 (1973) 921.
[15] E.R.G. Eckert, R.M. Drake, Analysis of Heat and Mass transfer, McGraw Hill
Kogakusha, New York, 1972.
[16] M.S. Malashetty, S.N. Gaikad, Effect of cross diffusion on double diffusive in the
presence of horizontal gradients, Int. J. Eng. Sci. 40 (2002) 773787.
[17] L.B. Benano-Melly, J.P. Caltagirone, B. Faissat, F. Montel, P. Costeseque,
Modeling Soret coefcient measurement experiments in porous media
considering thermal and solutal convection, Int. J. Heat Mass Transfer 44
(2001) 12851297.
[18] A. Postelnicu, Inuence of chemical reaction on heat and mass transfer by
natural convection from vertical surfaces in porous media considering Soret
and Dufour effects, Heat Mass Transfer 43 (2006) 595602.
[19] M.A. Mansour, N.F. El-Anssary, A.M. Aly, Effects of chemical reaction and
thermal stratication on MHD free convective heat and mass transfer over a
vertical stretching surface embedded in a porous media considering Soret and
Dufour numbers, Chem. Eng. J. 145 (2008) 340345.
[20] F.S. Ibrahim, F.M. Hady, S.M. Abdel-Gaied, M.R. Eid, Inuence of chemical
reaction on heat and mass transfer of non-Newtonian uid with yield stress by
M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172 171
free convection from vertical surface in porous medium considering Soret
effect, Appl. Math. Mech. 31 (2010) 675684.
[21] J. Szekely, J.W. Evans, H.Y. Sohn, GasSolid Reactions, Academic Press, New
York, 1976.
[22] M.C. Li, Y.S. Wu, Y.W. Tian, Y.C. Zhai, Non-thermal equilibrium model of the
coupled heat and mass transfer in strong endothermic chemical reaction
system of porous media, Int. J. Heat Mass Transfer 50 (2007) 29362943.
[23] F. Patisson, M.G. Francois, D. Ablitzer, A non-isothermal, non-equimolar
transient kinetic model for gassolid reactions, Chem. Eng. Sci. 53 (1998)
697708.
[24] S.R. DeGroot, P. Mazur, Non-Equilibrium Thermodynamics, North-Holland
Pub, Amsterdam, 1962.
[25] T. Rajeswara Rao, D.J. Gunn, J.H. Bowen, Kinetics of calcium carbonate
decomposition, Chem. Eng. Res. Des. 67 (1989) 3847.
[26] S.V. Patankar, Numerical Heat Transfer and Fluid Flow, McGraw-Hill Book Co.,
New York, 1980.
[27] W.Q. Tao, E.M. Sparrow, Transportive property and convective numerical
stability of the steady-state convective-difference equation, Numer. Heat
Transfer 11 (1987) 491497.
172 M. Li et al. / International Journal of Heat and Mass Transfer 67 (2013) 164172

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