International Journal of Hydrogen Energy 26 (2001) 551–558

www.elsevier.com/locate/ijhydene

Water–gas shift reaction over porous catalyst: temperature

and reactant concentration distribution
Menderes Levent ∗
Department of Chemical Engineering, Faculty of Engineering, Ataturk University, 25240 Erzurum, Turkey

Abstract
This work represents the results of the theoretical study of the distribution of concentration and temperature in porous
catalyst, carried out over spherical iron oxide=chromia catalyst pellets for the water–gas shift reaction (WGSR). The kinetic
information has been taken from an earlier study (G.C. Chinchen et al., Appl. Catal., 12 (1984) 97) for the above reaction.
The mass and heat transfer distribution coupled with chemical reaction, outside and within the catalyst particles for water–gas
shift reaction was estimated in this present study. A computer program was written to calculate both concentration pro6le and
temperature pro6le for the water–gas shift reaction. ? 2001 International Association for Hydrogen Energy. Published by
Elsevier Science Ltd. All rights reserved.

Keywords: Water–gas shift reaction; Temperature pro6le; Concentration pro6le; Spherical catalyst

1. Introduction description of the factors that determine the e:ectiveness of

In order to understand transport phenomena in porous
media, one may study 9uid 9ow with chemical reaction
through porous catalysts, particularly for the most important
chemical reactions, since in a major fraction of these, the
catalyst is a porous heterogeneous substance.
The phenomena of the catalysed reaction are important
in predicting reaction rates and the e:ect of the catalyst on
the conversion rate of the reactant. Nevertheless, transport
phenomena at the catalyst surface and within the catalyst
are still poorly understood. So, reactant concentration and
temperature distribution connected with catalyst particles
are calculated for the range of temperatures and pressures
of industrial application.
Mass transfer within catalyst structures was apparently
6rst analysed quantitatively by several workers [1–3]. The
earlier works were further developed by other workers [4 –
6]. The important result of these analyses is the quantitive
∗Tel.: +90-0442-231-2298; fax: +90-0442-233-1133.
E-mail address: levent62@yahoo.com (M. Levent).
porous catalysts.
In 6rst synthetic ammonia plant, carbon monoxide was re-
moved by liquefaction and scrubbing with hot caustic-soda
solution. Nitrogen was supplied from a cryogenic air sepa-
ration unit. However, it was soon realized that the carbon
monoxide liquefaction process was unsuitable for use on
such a large scale, and a catalytic process was developed
which converted carbon monoxide to carbon dioxide(and
additional desired hydrogen) by reaction with steam accord-
ing to the equation
CO + H2 O
CO2 + H2 (1)
This reaction was termed the “water–gas shift reaction”
(WGSR). The reaction was 6rst reported in the literature by
Mond et al. [7], in 1888.
1.1. Thermodynamics of water–gas shift reaction
The water–gas shift reaction is moderately exothermic
(GH = −41:1 kJ=mol) and hence its equilibrium con-
stant decreases with temperature, and high conversions are
favoured by low temperatures. The position of equilibrium

0360-3199/01/$ 20.00 ? 2001 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 3 6 0 - 3 1 9 9 ( 0 0 ) 0 0 1 1 6 - 6
552 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558

Nomenclature
ri radial coordinate in the centre of the
A; B constants of integration
catalyst (m)
C concentration of reacting component
r=R normalised distance (dimensionless)
(kmol=m3 )
R radius of the catalyst at the surface (m)
Ci concentration at the catalyst centre
R gas constant (kJ=kmol K)
(kmol=m3 )
Sh Sherwood number (dimensionless)
C0 concentration in the 9uid bulk (kmol=m3 )
T reaction temperature (K)
Cs concentration at the catalyst surface
T0 temperature at the bulk of the catalyst (K)
(kmol=m3 )
Ti temperature at the centre of the catalyst (K)
Ci =C0 concentration gradient (dimensionless)
Ts temperature at the surface of the catalyst
C1 integration constant
(K)
C1 ; C 2 adsorption equilibrium constants of compo-
V spherical-shell volume (m3 )
nents (1=bar)
D; De: e:ective di:usivity of the catalyst (m2 =s)
Greek letters
E i ; Et activation energies of reaction (kJ=mol)
GH heat of reaction (kJ=mol)
f; f; f 1st, 2nd and 3rd derivatives of a function
GHi enthalpy change of component i (kJ=mol)
F(r) function
Gr spherical-shell thickness (m)
hm mass transfer coeJcient (m=s)
GHR enthalpy change of a reaction (kJ=mol)
hT heat transfer coeJcient (W=m2 K)
; e: e:ective thermal conductivity (W=m K)
k reaction rate constant (1=s)
 Thiele modulus for the porous catalyst
k 1 ; k2 adsorption equilibrium constants for reac-
(dimensionless)
tants (1=bar)
 e:ectiveness factor (dimensionless)
k−1 ; k−2 adsorption equilibrium constants for prod-
ucts (1=bar)
Subscripts
Ki adsorption equilibrium constant of compo-
e: e:ective
nent i (1=bar)
i centre conditions of the catalyst
k1 rate coeJcient for reaction (1) (kmol bar
m mass
kg cat. h)
0 bulk conditions
Pi partial pressure of component i (bar)
s surface conditions
Q heat 9ux (kJ=s)
r rate of reaction (kmol=kg cat. h)
Superscripts
r radial coordinate or radius of the catalyst at
n iteration number
any position (m)
m; n; p; q stoichiometric coeJcients for reacting sub-
rs radial coordinate at the surface of the cata-
stances
lyst (m)

is virtually una:ected by pressure. Under adiabatic condi-
tions conversion in a single bed of catalyst is thermody-
namically limited as; the reaction proceeds and the heat
of reaction increases the operating temperature, and so re-
stricts the conversion possible. Typical carbon monoxide
levels that are achieved [8] at the exit with a single-adiabatic
bed of chromia-supported iron-based high-temperature(HT)
shift catalyst in an ammonia plant are in the range 2– 4%,
◦
within the temperature range 310 –450 C. The thermody-
namic equilibrium limitation on the reaction can be reduced
by using two or more beds of high temperature(HT) shift
catalyst with inter-bed cooling and, perhaps, removal of car-
bon dioxide between the stages.
A signi6cant improvement in the conversion of carbon
monoxide could then be obtained with a two-bed opera-
tion, with the second bed operating at the lowest possible
◦
inlet temperature, which in practice was about 200 –250 C.
The conventional iron-based catalysts are not suJciently
active for such low temperature operation, but low temper-
ature(LT) water–gas shift catalysts are, and when they are
used in the second bed, carbon monoxide exit concentra-
tions as low as 0.1– 0.3% can be achieved, an acceptable
economic level for subsequent methanation.
1.2. Kinetic model for the water–gas shift reaction
1.2.1. Kinetcis over high temperature(HT) shift catalyst
Numerous kinetic studies of the water–gas shift reaction
over iron oxide=chromia catalysts have been reported, and
more than 20 di:erent kinetic equations have been proposed.
Di:erences among authors have been especially marked in
their opinion of the reaction mechanism, and the e:ect of
 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558 553

pressure on the reaction rate. The reasons for this con9ict value of 121.8 kJ=mol deduced from semitechnical experi-
have been attributed to the presence of impurities [9] in the ments with the same catalyst. Their results indicate that sim-
gases used, to varying degrees of mass-transfer limitation ple 6rst-order reaction can be deduced from the Arrhenius
[10] and to the fact that kinetic measurements have been plot.
mostly obtained with integral rather than di:erential reac-
tors which were often operating only at or near atmospheric 1.2.2. Kinetics over low temperature(LT) shift catalyst
pressure. Fott et al. [11] asserted that the e:ect of pressure Much less publications have appeared on the mech-
on the reaction rate is the main criterion which enables the anism and kinetics of the water–gas shift reaction
suitability of a given kinetic equation to be evaluated. over copper-based catalysts than over high temperature
The 6rst systematic attempt to combine rate equations and iron-based catalysts, but similar types of kinetic expres-
reaction mechanisms was made by Kulkova and Temkin [14] sions have been proposed. Indeed, the pore di:usion lim-
who used a pure iron oxide catalyst prepared by precipitation ited version of the Langmuir–Hinshelwood Eq. (7) for
of iron nitrate with ammonia. copper-based shift catalysts is consistent with plant data
Experiments on the continuous catalytic water–gas shift and semi-technical scale results [19].
reaction have been carried out by Hulburt and Vasan [15] k[CO][H2 O]1=2 (1 − [CO2 ][H2 ]=K[CO][H2 O])
in which they make full use of the principles of statistical Rate = : (7)
P 1=2 (1 + C1 [CO] + C2 [H2 O] + · · ·)
design to elucidate the reaction mechanism
k[H2 O] 1.3. Derivation of concentration pro8les with mass
r= : (2)
1 + K[H2 O]=[H2 ] transfer resistance
Kodama et al. [16] used an iron oxide catalyst containing
A 6rst-order irreversible reaction in a spherical catalyst
10% Cr 2 O3 . They arrived at an equation of the type
particle can be represented when the reaction A → B occurs.
k{[CO][H2 O] − [CO2 ][H2 ]=K} A material balance for the reacting component over an ele-
r= : (3)
1 + K1 [CO] + K2 [H2 O] + K3 [CO2 ] + K4 [H2 ] ment of catalyst volume leads to a second-order di:erential
equation. For spherical catalyst particles, when steady state
This expression was put in relation to a steady-state mech-
conditions have been reached, the equation may be derived.
anism(without a rate-determining step) in which reaction
Mass di:usion into the spherical particle at radius r is
occurs between the gaseous components and reduced and
oxidized surface sites. @C
F(r) = −4r 2 D : (8)
Glavachek et al. [14]; Kul’kova and Temkin [17]; Shchi- @r
brya et al. [18] derived the following rate expression on the The expansion of the function F(r) by using Taylor’s theo-
basis of oxidation–reduction model: rem is
k1 k2 {[CO][H2 O] − [CO2 ][H2 ]=K} h2 
r= ; (4) F(r + h) = f(r) + hf (r) + f (r)
k1 [CO] + k2 [H2 O] + k−1 [CO2 ] + k−2 [H2 ] 2!
Podolski and Kim [11]; Fott et al. [12] and Chinchen et h3 
+ f (r) + · · · : (9)
al. [13] carried out experiments in recycle reactors and used 3!
statistical techniques to discriminate between rival models. On applying Taylor’s theorem to Eq. (8),
They also re-examined some of the previously published @C
data, and concluded that only Langmuir–Hinshelwood and f(r + Gr) = 4r 2 D
@r
the power-law model could adequately accommodate all of

the experimental results. @ @C
+4DGr r2 + 0((Gr)2 ): (10)
Langmuir–Hinshelwood: @r @r
kKCO KH2 O {[CO][H2 O] − [CO2 ][H2 ]=K} A mass balance over the shell of catalyst Gr is
r= :
{1 + KCO [CO] + KH2 O [H2 O] + KCO2 [CO2 ] + KH2 [H2 ]}2
Rate of di:usion into element
(5)
=rate of di:usion out of element
Power law [9,12,17]: +rate of chemical reaction


r = ak[CO]m [H2 O]n [CO2 ]p [H2 ]q ; (6) @C @ @C
4r 2 D + 4DGr r2 + 0((Gr)2 )
@r @r @r
Chinchen et al. [13] studied the kinetics of high-tempera-
@C
ture shift catalyst from experiments with a semi-technical =4r 2 D + 4r 2 GrKC: (11)
unit and a microreactor system under relevant industrial @r
conditions combined to give consistent kinetics parameters. After simplifying, we obtain


They estimate the activation energy to be 129:4±2:1 kJ=mol 1 @ 2 @C k
r = C; (12)
from microreactor experiments, in good agreement with the r 2 @r @r D
554 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558

where r is the radial co-ordinate, C is the concentration of 1.4. Estimation of temperature pro8le in catalyst pellets
reacting component, k is the reaction velocity constant and
D is the e:ective di:usivity. On di:erentiating Reaction with mass and heat transfer occurs simulta-
2 neously at any position within the pellet. The resulting
@C 2 @C k
+ = C: (13) intrapellet concentration and temperature gradients cause
@r 2 r @r D
the rate to vary with position.
The di:erential equation describing 6rst-order reaction and The energy balance for a spherical catalyst is
di:usion in the spherical particle, puts
@2 T 2 @T kC
+ = GH; (17)
V = Cr; @r 2 r @r e:

then where GH is the heat of reaction, k the reaction rate

constant, e: the e:ective thermal conductivity, and r the
V particle radius.
C= :
r The solution of Eqs. (17) and (13) with these boundary
By substituting in Eq. (13), we get conditions gives the temperature pro6le within the pellet.
Eliminating kC from Eqs. (13) and (17) yields
@2 V k 2

− V = 0: @C 2 @C e: @2 T 2 @T
@r 2 D De: + = + ;
@r 2 r @r GH @r 2 r @r
This di:erential equation has the solution

    @ 2 @C e: @ 2 @T
k k De: r = r : (18)
V = Cr = A exp r + B exp − r ; (14) @r @r GH @r @r
D D
By integrating Eq. (18) once using the following boundary
where A and B are constants of integration. Eq. (10) is solved conditions:
for the boundary conditions:
@C
(1) the concentration is 6nite at the centre of the sphere = 0; r = 0;
@r
(r = 0, CA = 6nite); (2) at the external surface of the catalyst
pellet, @T

 = 0; r = 0;
@C @r
r = R h(C0 − Cs ) = D ;


@r r=R @C e: @T
De: r 2 = r2 + C1
because the mass 9ux from the bulk to the catalyst surface @r GH @r
is equal to the di:usion 9ux within the pellet. Applying the
and then integrating a second time using the following
boundary conditions on Eq. (14) to get the concentration
boundary conditions:
pro6le in the catalysed reaction for the spherical catalyst
particle, C = Cs ; r = rs ;
C
=
C0 T = Ts ; r = rs ;

k
sinh D
r
    : (15) one obtains
[ Rr sinh k
D
R + hDr
mR
k
D
cosh k
D
R − hmDrR2 sinh k
D
R] GH
De: (Cs − Ci ) = (Ts − Ti ): (19)
e:
Eq. (15) shows that the concentration pro6le depends only
upon dimensionless parameters, the Thiele modulus , the This result, originally derived by Damkoehler [2], is not
Sherwood form of hm R=D, and the normalised distance r=R. restricted to 6rst-order kinetics, but is valid for any form of
Here, C0 is the concentration in the 9uid bulk, kmol=m3 , hm rate expression and it shows that the maximum temperature
is the mass transfer coeJcient, m=s, De: the e:ective dif- rise depends on the heat of reaction, transport properties of
fusivity of the catalyst, m2 =s, k the reaction velocity con- the pellet, and the surface concentration of the reactant.
stant, 1=s, R the radius of the catalyst at the surface, m, and The boundary conditions in the presence of surface resis-
r = radius of the catalyst at any position, m. tance to heat of mass 9ow are
The e:ectiveness factor in terms of Thiele modulus and
Sherwood number, Sh is r = rs ; hT (T0 − Ts ) = GHhm (C0 − Cs );
 

3  coth  − 1 @T GHDe: @C
= 2 1
: (16) r = ri :
 1 + Sh ( coth  − 1) @r e: @r
 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558
Therefore, the general solution is
GHDe: GHhm
T(x; y; z) = C(x; y; z) + T0 − C0
e: hT
hm De:
+Cs(x; y; z) GH − : (20)
hT e:
This equation was used in a computer program to estimate
the temperature pro6le at di:erent values of the Thiele mod-
ulus.
1.5. Estimation of extraparticle concentration and
temperature di:erences
At steady state the reaction rate expressed per unit mass
of pellet, may be written either in terms of di:usion rate
of bulk gas to the surface or in terms of the product of the
rate that would have been determined if the concentration
in the particle were uniform and e:ectiveness factor would
be taken into account:
r = Ahm (C0 − Cs ) = VkCs ; (21)
where C0 and Cs are the concentration in the bulk gas
and surface, respectively, hm is the mass transfer coeJcient
between bulk gas and solid surface, and A is the external
surface area per unit mass of the pellet. V is the catalyst
volume,  is the e:ectiveness factor, and k is the reaction
rate constant.
The temperature di:erence between 9uid, T0 , and surface,
Ts , can be represented in terms of heat transfer rate from
the bulk to the pellet in the case of an endothermic reaction,
or from the pellet to 9uid bulk in the case of exothermic
reaction,
Q = AhT (T0 − Ts ) = VkCs GHR ; (22)
where Q is the heat 9ux, hT is the heat transfer coeJcient
and GHR is the enthalpy of a reaction.
The formulae below are solved in a sequential estimation
procedure in which the estimations are continually updated.
The formulae are for concentration distribution
Ahm (C0 − Csn ) = Vn−1 k n−1 Csn ; (23)
where the e:ectiveness factor  is given by Eq. (16) and
the reaction velocity constant k is estimated at the surface
temperature Ts . It is supposed that the particle is isothermal.
The equation for the surface temperature is
AhT (T0 − Tsn ) = Vn−1 · k n−1 Csn GHR ; (24)
where the superscripts in Eqs. (23) and (24) identify the
iteration number.
These formulae are iterated to convergence using suc-
cessive substitution. Once convergence has been obtained,
the surface temperature corresponding to the converged val-
ues is given by Eq. (24) and surface concentration by Eq.
(23). Even at high temperatures the pro6le of temperature is
essentially isothermal, and therefore the method of calculat-
ing temperature and composition pro6les is valid.
555
Fig. 1. Internal temperature di:erences at various bulk temperatures
(Ts − Ti ) K, at  = 0:21 W=(mk).
2. Results and discussion
In this study the reaction conditions have been taken as:
total pressure of the process is 31 bar, carbon monoxide
partial pressure is 3 bar, steam partial pressure is 16 bar,
hydrogen partial pressure is 8 bar, and carbon dioxide partial
pressure is 4 bar. The temperature range was taken to be
◦
250 –450 C.
We have applied in this study kinetic information
on the water–gas shift reaction over commercial iron
oxide=chromia catalyst mainly taken from Chinchen et
al. [13,20]; they found that kinetics is best described by
the Langmuir–Hinshelwood model. On the basis of the
experimental work carried out on a semi-technical plant
at pressures up to 30 bar they found that the reaction is
signi6cantly pore-di:usion limited in 8.5 mm pellets at
◦
temperatures above 350 C. The reaction of water–gas shift
over a spherical catalyst has been assumed initially to
be an isothermal reaction. This hypothesis may be tested
for temperature pro6les, since signi6cant deviations from
isothermality in temperature pro6les will mean that the
hypothesis is not correct.
Fig. 1 shows the variation of the temperature di:erences
between the surface and the interior of the catalyst particles
with bulk temperature for the thermal conductivity value of
0.21 W=(mK) for iron oxide=chromia catalyst. Fig. 1 shows
that at that value of thermal conductivity, the temperature
◦ ◦
di:erence is a minimum of −4:5 C at 440 C. It also shows
that temperature di:erences become less at the industrial
◦
range of temperature between 365 and 540 C. Hence, the
reaction is essentially isothermal within the range of indus-
trial application. It is clear that the hypothesis of an isother-
mal pellet is satisfactory. The value of thermal conductivity
is reported by Chinchen et al. [13,20].
The external temperature di:erences are shown in Fig. 2,
◦
small at temperatures below 340 C, but increasing with bulk
◦ ◦
temperature to reach 55 C at 540 C. Fig. 3 shows temper-
ature pro6le with bulk temperatures which has been found
from Eq. (20). The lines marked (1 ), (2 ) and (3 ) show
that the temperature within the catalyst is constant from the
556 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558
Fig. 2. External temperature di:erences at various bulk tempera-
tures, at  = 0:21 W=(mk).
Fig. 3. Temperature pro6les in a porous spherical catalyst, at di:er-
ent values of the Thiele modulus (1 = 3:5; 2 = 9:64; 3 = 26:89)
and  = 0:21 W=(mk).
Fig. 4. Temperature ratio in a porous spherical catalyst, at
(1 = 0:53; 2 = 1:48; 3 = 3:98; 4 = 8:87; 5 = 19:75) and at
 = 0:21 W=(mk).
centre to a region close to the catalyst surface followed by
small di:erences within the surface region.
The dimensionless temperature distributions T=T0 are
shown in Fig. 4 at di:erent values of Thiele modulus and
e:ectiveness factor as indicated in the curves of this 6gure.
Fig. 5 shows the overall temperature di:erences at intra-
particle thermal conductivity value of 0.21 W=(mK). It is
clear that the overall temperature di:erences in dimension-
less form are decreased with 9uid temperature.
Fig. 5. The overall temperature di:erences at various bulk temper-
atures, at  = 0:21 W=(mk).
Fig. 6. Reaction rate constant versus experimental bulk tempera-
tures, at  = 0:21 W=(mk).
The logarithm of reaction rate constant versus experi-
mental bulk temperatures at thermal conductivity value of
0.21 W=(mK) is shown in Fig. 6. As seen in this 6gure, the
logarithm values of reaction rate constant increase linearly
with bulk temperatures. The reaction rate constant has been
extrapolated from the experimental results of Chinchen et
al. [13,20].
Arrhenius plots for the reaction water–gas shift are shown
in Fig. 7 in which the upper curve(1) shows the dependence
of the intrinsic reaction velocity constant upon exp(1=T ).
The gradient of the line is related to the activation energy for
the reaction, and it is a matter of considerable interest that
at low temperatures to the right of the graph, the activation
energy is 129:4 kJ mol, a value that is clearly identi6ed with
chemical reaction being the rate-limiting step. However, to
the left of the graph, there is a fall in activation energy
because the rate-limiting step is that of adsorption of reactant
on the catalyst surface.
The variation of the Thiele modulus for water–gas
shift with bulk temperature is shown in Fig. 8, where the
Thiele modulus is seen to increase exponentially with bulk
temperature.
The e:ectiveness factor is expressed by Eq. (16) and
is plotted against the Thiele modulus in Fig. 9. Values of
 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558
Fig. 7. Arrhenius plots for a porous spherical catalyst, the upper
curve(1): shows dependence of the intrinsic reaction rate constant
upon exp(1=T ), the lower curve(2): shows adsorption of reactant
on the catalyst surface.
Fig. 8. Thiele modulus versus bulk temperatures, at
 = 0:21 W=(mk).
Fig. 9. E:ectiveness factor for a porous spherical catalyst, at
 = 0:21 W=(mk).
e:ectiveness factor have been reported in the Catalyst Hand-
book [21] for a relatively large catalyst particle size used in
industrial water–gas shift.
The concentration pro6le within the catalyst body has
been found from Eq. (15) as described previously and Fig.
10 shows the concentration pro6les against dimensionless
◦ ◦
distance r=rs . The second curve at a temperature of 300 C
with a value of Thiele modulus = 1:17, and e:ectiveness
factor = 0:92, shows that there is no di:usion limitation at
this temperature.
557
Fig. 10. Concentration distribution in a porous spherical cata-
lyst at various Thiele modulus values and e:ectiveness factors
(1 = 0:36; 1 = 0:99; 2 = 1:17; 2 = 0:92; 3 = 3:23; 3 = 0:64;
4 =7:98; 4 =0:32; 5 =18:45; 5 =0:15) and at =0:21 W=(mk).
Fig. 11. External concentration di:erences at various bulk temper-
atures, at  = 0:21 W=(mk).
Pore di:usion limitation becomes more pronounced at
◦
temperatures above 400 C. Lines (4) and (5) in Fig. 10
◦
correspond to 400 and 450 C for which the values of the
Thiele modulus are 7.98 and 18.45, respectively, and the
values of e:ectiveness factor are 0.32 and 0.15, respectively.
The result of this work agrees with the studies of Chinchen
et al. and Twigg [13,20,21]. Fig. 11 shows the external con-
centration di:erences against various bulk temperatures. As
seen on this 6gure, the external concentration di:erences
are increasing exponentially to a value of 8 with increases
in bulk temperatures. The external concentration di:erences
are not signi6cant at low temperatures since they are less
◦
than 9:646 × 10−6 kmol=m3 below 250 C.
Di:usion limitation is more pronounced with an increase
in temperature as shown in Fig. 12, which clearly shows
the fall in concentration at temperatures in the range 350 –
◦
540 C. The intraparticle concentration di:erences increase
at a bulk temperature of 390 C as shown in Fig. 12, but
after that, it decreases because of the reduction in surface
◦
concentration to reach 36.97 at 540 C, when concentration
at the centre is 3:1451 × 10−30 .
558 M. Levent / International Journal of Hydrogen Energy 26 (2001) 551–558
Fig. 12. Internal concentration di:erences at various bulk temper-
atures, at  = 0:21 W=(mk).
Fig. 13. The overall concentration di:erences at various bulk tem-
peratures, at  = 0:21 W=(mk).
Fig. 13 shows the overall concentration di:erences at var-
ious bulk temperatures above. It is clear that the overall
◦
concentration di:erences are becoming constant 390 C bulk
temperatures above.
3. Conclusions
From this result the external temperature di:erences are
large compared with intraparticle temperature di:erences at
high 9uid temperature. Heats of reaction have considerable
e:ect on the internal temperature di:erences. When the heat
of reaction is large, intraparticle temperature gradient may
have larger e:ect on the reaction rate than the concentration.
Even when GH is low the centre and surface temperature
may di:er appreciably, because catalyst pellet may have a
low thermal conductivity.
The maximum temperature di:erence between surface
and interior is about 4 –9 K at the highest reaction rate, while
the external temperature di:erences between the 9uid and
surface temperatures are of the order of 100 K.
Intraparticle concentration di:erences have been esti-
mated in this work, by 6nding the concentration at the cen-
tre of the catalyst from the Eq. (15) as shown previously.
At low bulk temperatures, the reaction rate constant will be
small, the Thiele modulus will be low, and the e:ectiveness
factor will be high, therefore the intraparticle concentration
◦
di:erences is small and can be neglected below 265 C.
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