Chemical Engineering and Processing, 32 ( 1993) 117- 189 177

Steam reforming and methanation effectiveness factors using the dusty

gas model under industrial conditions

S. S. E. H. Elnashaie* and M. E. E. Abashar

Chemical Engineering Department, College of Engineering, King Saud University, PO Box 800, Riyadh 11421 (Saudi Arabia)

(Received October 5, 1992)

Abstract

A rigorous mathematical model based on the dusty gas model is developed to investigate the phenomenon of
diffusion and chemical reaction in porous catalyst pellets for the steam reforming and methanation reactions under
industrial conditions. Two simplified Fickian type diffusion reaction models are also developed and their results are
compared with the results of the rigorous model. Parametric investigations on the single catalyst pellet are carried
out using the dusty gas model as well as the simplified models in order to obtain a deeper insight into these complex
catalytic gas-solid systems and to explore regions of applicability of the simplified models. The phenomenon of
negative effectiveness factors is also investigated.

Introduction Strange-looking effectiveness factor profiles along the

Industrial catalysts are usually in the form of porous
pellets and most of the active surface is internal; hence,
the rate of reactions and selectivity are usually strongly
influenced by the diffusion rates of reactants and prod-
ucts inside the catalyst pellet.
The reaction mixture in practical situations is usually
composed of several components. This multicomponent
mixture must diffuse through a tortuous complex net-
work of pores ranging from micropores to macropores.
It is therefore subjected to different diffusional resis-
tances which can be described by diffusion laws of
varying degrees of sophistication and rigor. Flux rela-
tions for multicomponent mixtures are essential for the
accurate modeling of these systems. The literature con-
tains numerous studies based on simple flux relations
for material balance equations which are strictly valid
only for binary mixtures or for treating simple cases of
dilute components diffusing in a large excess of another
gas. The dusty gas model gives the simplest effective
method available for rigorously describing diffusion of
multicomponent mixtures in the intermediate region,
where all modes of transport are significant [ 11.
The theory of simultaneous diffusion and chemical
reaction in porous catalyst pellet is very well developed
for single irreversible reactions [2]. However, the theory
is not at all well developed for the multiple reversible
reactions.
*Author to whom correspondence should be addressed.
length of the catalyst tube were obtained by many
investigators [3-61 for the multiple reversible-reaction
system of steam reforming of methane. Soliman and
Elnashaie [7] presented a simple explanation for this
phenomenon using simplified linear kinetics. In this
study a detailed analysis is performed to investigate
diffusion and chemical reaction in porous catalyst pel-
lets for the steam reforming and methanation reactions
under industrial conditions using a general and reliable
kinetic model developed by Xu and Froment [8]. The
rigorous dust gas model is rarely used in literature
[9, 101 whereas simplified models are widely used
[4, 111. The purpose of this investigation is actually
threefold: first, to obtain accurate results using the
rigorous dusty gas model for the effectiveness factor
under industrial conditions at elevated temperatures;
second, to evaluate regions and limits of applicability of
the simplified models using a rigorous dusty gas model
as a basis for this evaluation; and third, to explain the
phenomena of negative and erratic behavior of the
effectiveness factors associated with this type of reac-
tion network. Due to the generality of the kinetics of
Xu and Froment [8], the model is also used to investi-
gate the behavior of methanation reactions. Parametric
investigations on the single catalyst pellet are carried
out using the dusty gas model as well as the simplified
models. The present investigation differs fundamen-
tally from that of Xu and Froment [4] who used a
Fickian type diffusion reaction model and from that of
Haynes [9] who, although using a dusty gas model,
restricted his investigation to the low temperature

02552701/93/$6.00 0 1993 - Ekvier Sequoia. All rights reserved

178

range (because of numerical difficulties associated with The kinetic rate coefficients and adsorption equilibrium
the shooting technique for the solution of the nonlinear constants are given by Xu and Froment [S] and
two point boundary value differential equations) which Abashar [17]. The net rates of methane and steam
is less important from both practical as well as funda- disappearance are given by
mental points of view compared with the high tempera-
ture range covered in the present investigation. (5)

(6)

Rate expression The net rates of formation of hydrogen, carbon monox-

ide and carbon dioxide are given by
The literature contains large numbers of kinetic mod- r H2 = 3r, + 111+ 4r,,, (7)
els for stream-methane reactions and consequently
different rate expressions are available. A comprehen- rco = rI - rn (8)
sive review of steam reforming kinetics has been re-
ported by Elnashaie et al. [ 121. Xu [ 131 and Elnashaie et rcoz = rlT + rm (9)
al. [ 121 have given a detailed tabulation of the condi-
tions and the results of kinetic studies in the literature.
Development of models
The differences between the rate expressions in some
cases are due to the fact that some of the rate expres-
sions are obtained for regions of parameters where the The mathematical models are developed for the rig-
reactions show positive effective order dependence of orous dusty gas model as well as the simplified models
the reaction rate with respect to steam [3] while others I and II. The simplified models cannot be derived on a
are for regions of parameters where the reaction shows rigorous basis [ 181; however, they are widely used and
a negative effective order dependence with respect to much simpler to solve [4, 11, 191. The aim of including
these two widely used simplified nonrigorous models in
steam [ 14,151. Xu and Froment [8] have developed new
the investigation is to find the limits of their applicabil-
and more general and realistic intrinsic rate equations
for the steam reforming of methane using an integral ity without introducing gross errors in the simulation.
The correct basis of comparison is obviously the rigor-
flow reactor and a commercial catalyst (Haldor Topsere
Ni/MgAl,O, spinel). The nonmonotonic nature of these ous dusty gas model.
rate equations has been shown by Elnashaie et al. [ 161.
Dusty gas model
Xu and Froment [8] used Langmuir-Hinshelwood
(Hougen- Waston) principles with a mechanism of thir- Mason and Malinauskas [ 11, by using the dusty gas
teen steps, three of which are rate determining steps and model, were able to obtain a single equation for the
total diffusive flux:
ten occur at equilibrium.
Rate expressions for a reaction network consisting of T
yN -yiN
three representative reactions for the steam reforming -gradC.=$,+ c 1kL (10)
j#i 1,
of natural gas were obtained:
The effective diffusivity of any component (D;) can be
CH, + Hz0 =3H,+CO (I) obtained from eqn. (10) by dividing its flux by the
CO + H,O =H,+CO, (II) negative of its concentration gradient:

CH, + 2H,O + 4H, + CO, (III) 1 -grad Ci

(11)
0; Ni
The corresponding rate expressions are
Of course, the equation predicted by the dusty gas
model ( 10) can be extended to include the fluxes caused
by other driving forces such as thermal diffusion, forced
diffusion, etc.

Simpl$ed model I
Equation (10) resulting from the rigorous model
(dusty gas model) for diffusion is not as easy to imple-
where ment and to solve as simplified Fickian type models.
Some investigators [4, 5, 11, 17, 191 used simplified
DEN = 1 f Kcopco + &PH~ + &H~PcH.,
equations for the flux relations. The ordinary diffusion
+ &IZOPHZOIPH> (4) terms in eqn. (10) are approximated by
 179

(6) Diffusion takes place by Knudsen and ordinary

(12) diffusion [ 91.
(7) Isothermal conditions are assumed [ 161.
Equation (10) becomes a simplified equation of the
(8) The concentration profiles are symmetrical about
form
the center of the pellet [ 211.
Ni = -0; grad Ci (13) Steam reforming of methane is a six-component sys-
tem (CH,, H,O, H,, CO, CO,, N2) in which five
where
components (CH,, H,O, H,, CO, COz) participate in
two or more chemical reactions (I, II, and III).
(14) A differential mass balance on the ith component of
the steam reforming in a catalyst pellet of slab geometry
D&, is obtained from the Wilke equation for diffusion
gives the following equations:
of component i through other stagnant components of
the mixture [ 201:
5 = ki, YkiPPrk i=l,2,...,5 (19)
1
-= (15)
Dim The flux for the inert N, is equal to zero:
and the effective value of D, is equal to NN2 = 0.0 (20)

(16) Dusty gas model

7
Equations (10) and ( 19) form a set of ten simulta-
Of course, this Wilke equation is strictly valid only for neous first-order differential equations for CH4, HzO,
dilute systems, but can be used as an approximation for H,, CO, and CO2 with the following ten boundary
multicomponent systems. conditions which are split between points I = 0 and
I =I,:
SimpIiJied model II
Elnashaie et al. [ 191 used eqn. (12) to approximate at I= 0.0, Ni = 0.0
(21)
D& by at l=l,, c, = c;

(17) for i = 1,2, . . . , 5.

Equations ( 10) and ( 19) can be solved for ten un-
and then approximating the ratio of the fluxes by the knowns, five values for fluxes and five for concentra-
ratio of the rates of the reactions [II] to give tions, and the concentration of nitrogen is obtained by
difference. Since we have five components and two
Dt f Yj -Yi?/li) independent stochiometric reactions, two dependent
(18)
m7 jti I variables are therefore enough to describe the system
and the rest of the components can be obtained from
implicit stochiometric relations. Therefore the system of
Mass balance differential equations for the fluxes (eqn. (19)) is re-
duced to two differential equations and three algebraic
The combined flux relations of the dusty gas model stochiometric equations. The main reactants (methane
( 10) and simplified models ( 13) are supplemented by and steam) for the steam reforming of natural gas are
the mass balance equations to determine the concentra- selected as key components. The flux equations of
tion profiles of the reacting species and the effectiveness methane and steam are given by
factors for a single catalyst pellet under the following
assumptions.

Model assumptions
dN,,,
( 1) The reaction mixture is an ideal gas [9]. - = -p&r + rII + 2r,&
dw
(2) The system is at steady state.
(3) The catalyst pellets are assumed to be a slab with The characteristic length Z, [2] is given by
characteristic length Z, [ 21.
(4) External mass and heat transfer resistances are
negligible [5, 161.
(5) Viscous flow is negligible and hence the pellet is The stoichiometric relations for the components H,,
under isobaric conditions [IO]. CO, and CO2 are obtained by simultaneous elimination
 180

of the rates of reactions I, II, and III from the set of the
five differential equations (19) to give three algebraic
equations:
0;
NnZ = - NnZo - 2&n_, (25a) a,= (D;*)S

Nco = &I*0 - 2Ncn, (25b) The equations for the catalyst pellet in the final form
can be summarized as
N co* = - Nn20 + NCH, (25c)
dA .
Normalizing to obtain dimensionless rates of reaction -L%+ = - 42RCH,pp
dw
for methane and steam by considering the net rate of
reaction of steam at the surface of the catalyst pellet as
dAHzo = -q52RH20pp
a reference value, dw

R
r1 + r111 AI1= -&o - 2&
(26)
cH4 = (r, + r,, + 2r,,,)S
&o = &I20 - 242,
r1 + TII+ 3.11,
R (27) aco, = - ko + &x4
H20 = (I, + r,, + 2r,,,)
a,, = 0.0 (41)
and using the following dimensionless relations,

(42)
(28)
with the boundary conditions
(2% w = 0.0, a,= 0.0
(43)

1
4 = l (II + TII + 2r,,,Y ID- w = 1.0, rr,=n;
c (30)
CD where i = 1,2, . . . . , 5.
where D is the characteristic diffusional coefficient de-
fined by Simplified models I and II
By insertion of the flux relations (13) into the mate-

i=(&+&-) (31) rial balance equation (19), a set of five nonlinear sec-
ond-order boundary value differential equations for
and 1 and 2 refer to steam and methane, respectively. CH,, H,O, H,, CO, and CO, are obtained:
C is the total concentration at the surface and is given d2C
by
_I
i=l,2,...,5
d12
PS
C=L- with the boundary conditions
(32)
RT
dC-
Equation (10) can also be normalized by defining the I = 0.0, 2 = 0.0
dl
following relations: (45)
l=l,, Ci = C;
G
ni =-
(33) Using dimensionless variables and parameters and
C
with methane and steam as key components, two sec-
ond-order boundary value differential equations for
(34)
methane and steam are obtained:
0 is the ratio of the ordinary diffusion resistance to the
Knudsen diffusion resistance. It follows that the Knud- (46)
sen, transition, and bulk diffusion regimes correspond
to 8 -+ 1, 8 = 1, and f3 % 1, respectively. (47)
Based on this normalization we obtain
with the boundary conditions
(35)
w =o.o, s
aw
=o.o
(36)
w = 1.0, 7r, =7t;
 181

with i = CH,, H,O, where intrinsic rates of production or consumption of the

1
(Y, + rrr + 2r,,,)* I2 specific components. The effectiveness factors of the
4 = 1, CD;
(49) components are the more relevant ones for complex
[ reaction networks. Both types of definitions for the
and 03 will be obtained from eqn. (14), and the effec- effectiveness factors are used in this paper with more
tive molecular diffusivity of component i in a multicom- emphasis on the effectiveness factors of the compo-
ponent mixture, DE,, , is obtained from eqns. (16) and nents. The effectiveness factors are functions of the
(18) for the simplified models I and II, respectively. diffusional resistances, rates of reaction under bulk
Three algebraic equations for hydrogen, carbon monox- conditions and the equilibrium constant for reversible
ide, and carbon dioxide are obtained by insertion of the reactions [22]. The evaluation of the effectiveness fac-
flux relations ( 13) into the stoichiometric relations (25) tors during catalytic reactor simulation taxes the com-
and the resulting first-order differential equations are putation with some extra effort. However, it is a very
normalized and integrated to give the dimensionless useful indicator of the effect of diffusional limitations
concentrations of hydrogen, carbon monoxide, and car- on the system. It gives, in one number, the effect of the
bon dioxide respectively: complex interaction between diffusion and reaction on
the behavior of the system.
xH2 = G, - & HZ
[DL,o(~H~o - +o)

- GHJI
+ ~DF_IH,(~cH, (50) Computational algorithm

no- = 7cgo - $ [ -DeH,o(s,o - G,o> The catalyst pellet equations resulting from using the
co
dusty gas model (39) -( 43) and simplified models I and
+ ~E~TL,(~ccH~
- %?x-IJI (51) II (46)-(48) are two-point boundary value problems
and are solved by the global orthogonal collocation
%02 = Go2 -& [DeH2~(n~2~-Gzo)
technique [21, 23,241. The results were first checked
co2
against the published results of Haynes [9] which were
-DEH,(QH,- ~&J (52) obtained by using the shooting technique. Details of the
The concentration of nitrogen is obtained by difference. efficient computation algorithms developed for both the
Similar equations for the catalyst pellet are obtained for dusty gas and the simplified models are given .by
methanation reactions by considering the rates of reac- Abashar [ 171.
tion in the reverse sense.

EfSectiveness factor Results and discussion

When the rate of reaction is large in comparison with
the rate of diffusion, the reaction is said to be limited by Since natural gas steam reformers typically operate in
diffusion. The effectiveness factor is used as a measure temperatures ranging from about 800 K to 1080 K, this
for diffusional resistances and for the ith component or high temperature range is covered in this study. Haynes
reaction is defined by [9] used a simpler kinetic model and restricted his study
of steam reforming of methane using the rigorous
yli =
model (dusty gas model) to lower temperature ranges
actual rate of reaction of component i (or reaction i) because of the numerical problems he faced by using
rate of reaction of component i (or reaction i) the shooting technique to solve the boundary value
at outer surface conditions differential equations of the catalyst pellet. Xu and

s ri (C, T, P) d Vp
= V,r,(C, T, P)
(53)
Froment [4] used a Fickian type model and did not
compare the results with a rigorous dusty gas model.
For the part dealing with the steam reforming of
methane, the base case for the bulk conditions and the
where the intrinsic rate of the reaction is the rate of parameters of the single catalyst pellet are obtained
reaction evaluated at external surface conditions of the from the work of Haynes [9] and are shown in Table 1.
catalyst pellet (since the external mass transfer resis- The Knudsen and binary molecular diffusivities are
tances are negligible in the problem under investiga- obtained from the work of Abashar [ 171.
tion). The effectiveness factor can be defined for
individual reactions using the ratio between the actual Effectiveness factors
and intrinsic rates of these reactions. It can also be Figures l(a) and (b) show the effectiveness factors,
defined based on components using the actual and intrinsic and actual rates of reaction profiles for reac-
182

1%
N I 30
P I 2500 kPo
SI M t 1.67
- DUSTV GAS MODEL
_-_-__sIMPLIFIEO MODEL 1 -----SIMPLIFIED MODEL I

800 900 1000 11IOC 800 900 1000 11

TEMPERATURE (IO TEMPERATURE (K)
lo, lOA&

Pz3500 kPa
SIM= 1.67
- DUSTY GAS MODEL
----- SIMPLIFIED MODEL I -2 ----- SIMPLIFIED MODEL I
t-61 I Id I I

800 900 1000 1100 800 900 1000 I100

TEMPERATURE (K) (4 TEMPERATURE (k 1

Fig. 1. For the dusty gas model and simplified model I: (a) effectiveness factor profiles of reactions I, II, and III; (b) effect oftemperature
on the intrinsic and actual rates of reactions I, II, and III; (c) effectiveness factor profiles of CH,, H,, CO,, and H,O; (d) effect of
temperature on the intrinsic and actual rates of reactions of H,, H,O, CH,. and C02.

tions I, II, and III obtained by using the dusty gas
model as well as the simplified model I.
The effectiveness factor profiles of reactions I and III
decrease continuously with the increase of temperature.
Reaction II is exothermic (AH = -41.15 kJ/mol) and
reversible, therefore the temperature has conflicting
effects on its intrinsic rate of reaction. Increasing the
temperature causes an increase in its forward rate and
thus tends to cause the intrinsic rate of reaction to
increase. On the other hand, for such an exothermic
reaction the increase in temperature causes the equi-
librium constant to decrease and thus tends to decrease
the intrinsic rate of reaction. The two conflicting effects
cause the rate of reaction dependenie upon temperature
to have a weak nonmonotonic behavior, as shown in
Fig. l(b). It is clear that the intrinsic and actual rates of
reaction II are moving towards each other asymptoti-
cally. Therefore, the effectiveness factor is clearly mov-
ing asymptotically towards unity. It exhibits a slight
decrease with a weak minimum at the early part of the
temperature range. The effectiveness factor profiles of
the simplified model I are quite close to those obtained
using the dusty gas model.
Figure l(c) presents the effectiveness factor profiles
for the components CH,, Hz, CO,, and H,O obtained
by the dusty gas model and simplified model I. Figure
l(d) shows their intrinsic and actual rate of reaction
profiles. Carbon monoxide profiles are excluded from
these Figures because they show different behavior and
will be discussed in detail in a separate paragraph. The
diffusional limitations for methane, hydrogen, steam,
and carbon dioxide generally increase with temperature
 183

TABLE 1. Bulk conditions and the parameters of the catalyst of - 29.0 kmol/(kg cat. h) while the actual rate of reac-
pellet [9] tion has an approximate value of -0.413 kmol/( kg
cat. 11). Therefore a small positive effectiveness factor is
Pressure 2500 kPa
Steam to methane ratio 1.67 obtained of a value equal to 0.01424 (Fig. 2(b)). The
(S/M) two rates of reaction behave nonmonotonically (Figs.
Gas composition 2(c) and (d)) and have negative minimum values. The
(mole fraction) decrease of the intrinsic rate of reaction is much faster
0.30
CH, than that of the actual rate of reaction. This behavior is
Hz0 0.50
0.05 reflected in the effectiveness factor profile in the temper:
HZ
co 0.05 ature range 800-900 K, but still gives positive values of
CD, 0.05 the effectiveness factor as shown clearly in Fig. 2(b). As
N* 0.05 the intrinsic rate of reaction approaches the actual rate
Catalyst pellet
of reaction from below, the effectiveness factor rises
Shape Raschig ring
Dimensions 15.875 mm x 6.35 mm x 9.525 mm sharply to a value of unity. Since the point of intersec-
Porosity c 0.362 tion d is in the negative domain of the reaction rates, a
Tcxtuosity t 3.000 positive effectiveness factor of a value equal to unity
Density pp 2338.0 kg/m (qco = 1.O) is obtained. After the intersection the intrin-
Mean pore radius ? 1600 8,
sic rate of reaction attains a small negative value of
Characteristic length I, 1.5875 mm
absolute value less than the absolute value of the actual
rate of reaction, giving a positive effectiveness factor of
a value greater than unity and this is shown clearly in
and the diffusional limitation for methane is very sensi- Fig. 2(a). After point d, the intrinsic rate of reaction
tive to temperature, especially at low temperatures. The becomes positive, while the actual rate of reaction is
simplified model I gives effectiveness factor profiles of still negative, resulting in a drastic drop of the effective-
the components which are quite close to those obtained ness factor to negative values (Figs. 2(a) and (b)). This
using the rigorous model profiles as shown in Fig. l(c). phenomenon, which occurs in the vicinity of the ther-
The effectiveness factor profiles of carbon monoxide modynamic equilibrium as shown in Figs. 2(c) and (d)
obtained by using the dusty gas model and the sim- and Table 2, is thus a real physical phenomenon and
plified model I are shown in Fig. 2(a). The effectiveness not a numerical artefact.
factor profile shows a strange phenomenon of fluctua- Two interesting observations are to be noticed in
tion from positive to negative values. The domain of Table 2.
fluctuation is magnified in Fig. 2(b). Since the actual (1) At 905.297 K (point d in Fig. 2(d)) the intrinsic
rate of reaction of carbon monoxide starts at low values rate of reaction reaches its thermodynamic equilibrium
and becomes almost horizontal (Fig. 2(c)), the domain and according to this situation the value of the effec-
of the actual and intrinsic rates of reaction correspond- tiveness factor should be equal to infinity. In the neigh-
ing to this phenomenon is also magnified in Fig. 2(d) to borhood of 905.297 K the intrinsic rate has very small
follow the behavior more closely. The intrinsic and absolute values, resulting in high absolute values of the
actual rates of reaction start with negative values at
800 K (Figs. 2(c) and (d)) and decrease to reach a TABLE 2. Intrinsic and actual rates of reaction and effectiveness
minimum negative value, after which both start to factors of carbon monoxide obtained by the dusty gas model in
increase continuously to change their signs and attain the temperature range 900%950 K
positive values. The negativity of the rate of reaction is
Intrinsic rate Actual rate
due to the complex interaction between the reversibili-
(TK) (kmol/kg cat. h) (kmol/kg cat. h) qco
ties of reactions I and II and thus the net rate of
reaction of carbon monoxide becomes merely a con- 900.0000 - 3.5050 - 0.2528 f0.0721
sumption rate rather than a production rate. The intrin- 905.0000 -0.1990 -- 0.2260 + 1.1336
sic and the actual rates of reaction intersect at point d 905.2900 -0.0050 - 0.2250 +45.0000
905.2970 0.0000 -0.2240
which has a value of -0.25 kmol/( kg cat. h) as shown
906.0000 +0.4712 ~ 0.2200 7 oq34668
in Figs. 2(c) and (d). At this point the effectiveness 907.0000 + 1.1442 -0.2143 -0.1873
factor of carbon monoxide should be equal to unity 908.0000 + 1.8197 - 0.2086 -0.1147
(+o = 1.0). On the left hand side of point d both rates 909.0000 +2.4978 ~ 0.2029 -0.0812
of reaction are of the same negative sign (Figs. 2(c) and 910.0000 +3.17X2 - 0.1970 -0.0620
920.0000 + 10.0947 -0.1366 -0.0135
(d)) and the intrinsic rate of reaction is much lower
939.6650 +24.1960 0.0000 0.0000
than the actual rate of reaction, for example, at 800 K 950.0000 +31.6084 +0.0716 f0.0023
the intrinsic rate of reaction has an approximate value _
 184

-
-----
=
N 30
P = 2500 kFb
S/U
DUSTY
-_ 1.67

SIMPLIFIED
G& MODEL
MODEL I
?
~_lOO-
1501
N = 30
P ~2500
SIM
kPo
: 1.67

_lOOl I I
800 900 1000 11
(a) TEMPERATURE (W) Cc) TEMPERATURE (K)
2I
N = 30
P ~2500 kPo
SIM I 1.67
DUSTY GAS MODEL l-
SIMPLIFIED MODEL 1 d

0
\I
Z d
-7
_I - d

N -30
-2 P ~2500 LPo
,WTRlWs.lC SIH = 1.67
DUSTY G& MODEL
_____ SIMPLIFIED HOOEL I
-3 t i
,
cLT I
-4, I I

800 900 1000 11 000 900 1000 11

(b) TEMPERATURE (K) (d) TEMPERATURE (K)

Fig. 2. For the dusty gas model and simplified model I: (a), (b) effectiveness factor profiles of CO; (c), (d) effect of temperature on the
intrinsic and actual rates of reaction of CO.

effectiveness factors, for example, at 905.290 K the are a real phenomenon and are neither numerical arte-
value of the effectiveness factor becomes equal to facts nor a result of certain simplifications of the mod-
45.0000. At 906 K the effectiveness factor has a negative els. Soliman and Elnashaie [ 71 have recently presented a
value of -0.4668. simple explanation for this phenomenon using sim-
(2) At 939.665 K (point d in Fig. 2(d)) the actual plified linear kinetics. They show that this behavior is
rate of reaction reaches its thermodynamic equilibrium basically due to the structure of the reaction network.
and the effectiveness factor becomes equal to zero. Elnashaie et al. [6] observe the same phenomenon of
Around this temperature we find that at 920 K the negative and erratic effectiveness factor profiles for
effectiveness factor has a small negative value intermediate components in the partial oxidation of
( -0.0135) and at 950 K it has a very small positive o-xylene to phthalic anhydride. They were also able to
value of 0.0023. prove analytically the existence of this phenomenon.
With regard to this complicated phenomenon the
simplified model I gives almost identical results to the Concentration pro$les
dusty gas model under the conditions used in these runs The terminal values of the temperature range (800
(Figs. 2(a)-(d)). The above results and discussion rep- and 1080 K) are selected to show the concentration
resent the physical and numerical proof that the effec- profiles of the components HZO, CH,, Hz, CO,, CO,
tiveness factor profiles along the length of the steam and Nz inside the catalyst pellet obtained by using the
reforming reactors obtained by the investigators [3-61 dusty gas model and the simplified model I (Fig. 3).
 185

_____
0.60
N ~30
r.s&l K T = 1080 K
Pz 2SOO kPa P = ZSOO kPa
0.50 S/M t 1.67

I
SI M = 1.67
DUSTY GAS MOOEL
0.4 SIMPLIFIED WOOEL I

20 0.40
0.40
t - DUSTV GAS MODEL
----- SIMPLIFIED MODEL I 0.30
0.35
t
a3 0.20
------ CH*
-___-___-_____-_

0.25 0.10 t---__--- ~"___---___.

4

O ?o.: DIMENSIONLESS CO_ORDINAlE OF THE PELLET I W

0.001
0.00 0.20 0.40 0.60 080 3
DIMENSIONLESS CO _ OftDINATE OF THE PELLET. w

0.16 0.35
--------___ Hz
N-30 --------.
P-_lSOO kPo
0.30 - N = 30 >\
t = IO80 K \
P = 2500 kPa I
0.11
0.25 - S/M = 1.67
- DUSTY GAS MODEL
-v-m-- SIMPLIFIED MODEL I

0.08 - DUSTV GAS MODEL

----- SIMPLIFIED MODEL I

t -MIXX
--FRICTION

0.04
ORFYE Ycu
4 FwcrIoN \
0.05 -
co
O.OC 1 I 1 I
0.00, I 1 I I
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

DIMENSIONLESS CO_ORDINATE OF THE PELLE1.W DIMENSIONLESS CO_ ORDINATE OF THE PELLET, W

Fig. 3. For the dusty gas model and simplified model I: concentration profiles of (a) H,O and CH, at 800 K, (b) CO,, H,, N,, and CO
at 800 K; (c) H,O and CH, at 1080 K; (d) H,, CO,, CO, and N, at 1080 K.

The concentrations of the components and their distri- TABLE 3. Bulk concentrations of the components at steam to
bution are highly affected by the increase of the temper- methane ratios of 5.0
ature. High temperatures favor the production of
Component Mole fraction
hydrogen. The rate of diffusion at high temperature,
which is the usual industrial condition, controls, and CH, 0.1333
the reactions are almost complete and reach their ther- Hz0 0.6667
modynamic equilibrium in a thin shell near the surface HZ 0.0500
of the catalyst pellet. It is clear that the concentration co 0.0500
CO, 0.0500
profiles of the two models show some differences.
N, 0.0500

Eflect of steam to methane ratio

Since a high steam to methane ratio is used widely in
industry to avoid carbon formation, the effects of in- model as well as the simplified models I and II are
creasing the steam to methane ratio to 5.0 on the implemented at those simulated industrial conditions.
effectiveness factors and rates of reaction are investi- Figures 4(a) and (b) show the effectiveness factor
gated. The bulk concentrations of the components at profiles of reactions I, II, and III obtained by the dusty
this ratio are summarized in Table 3. The dusty gas gas model and simplified models I and II at a steam to
 - DUSTY GAS MODEL N E 30
_-a SIMPLIFIED MODEL I P sZSDD kPo
________ SIMPLIFIED MODEL II - DUSTY GAS MODEL
--- SIMPLIFIED MODEL I
_ _ _ _ _ _ _ . SIMPLIFIED MODEL II

0.001 I I

000 SW 1000 1u
TEMPERATURE (K) Cc) TEMPERATURE (K)
U.0
- UJSTY GAS MODEL - DUSTY GAS MODEL
-_- SIMPLIFIED MODEL 1 ---- SIMPLIFIED MODEL 1
_______ SIMPLIFIED MODEL II ________ SIMPLIFIED MODEL II
=; 0.40-

6
&
ii! h ._._.-._.-.- co
- 0.00
z
:
g
i=
ti -o.uJ-

t
Y

z -0.80- N I 30
: P z 2500 kPo
I=: 1.5175 E- 3m
B
I
8 -1.20 I I
000 900 1000 1100 800 900 1000 11

TEMPERATURE (HI (4 TEMPERATURE (K)

Fig. 4. For the dusty gas model and simplified models I and II, S/M = 5: effectiveness factor profiles of (a) reaction I; (b) reactions II
and III; (c) H,, H,O, CH,, and CO,; (d) CO

methane ratio equal to 5.0. The models show the exis- The following are clear from these results.
tence of the interesting phenomenon of nonmonotonic (1) The erratic behavior and negative values of the
behavior of the effectiveness factor for reaction I. The effectiveness factor of some components indicate the
explanation for this behavior follows the same basis existence of a more general phenomenon which is not
presented earlier. There are large differences between confined to a certain range of steam to methane ratios.
the effectiveness factor profiles of reactions II and III (2) Although in some regions of parameters the sim-
obtained by the rigorous model (dusty gas model) and plified models give good estimations of the effectiveness
those obtained by the simplified models (I and II) as factors, this cannot be generalized. In other regions
shown in Fig. 4(b). of parameters the errors in estimating the effective-
The effectiveness factor profiles of the components ness factors using the simplified models can be quite
H,O, CH4, HZ, CO*, and CO at a steam to methane significant.
ratio of 5.0 are presented in Figs. 4(c) and (d) for the
dusty gas model and simplified models I and II. The
effectiveness factor profiles of all components obtained Methanation reactions
by the simplified models I and II show large deviations
from those obtained by the dusty gas model. The erratic The methanation reactions are the reverse of the
behavior of the effectiveness factor of carbon monoxide methane steam reforming reactions. The generality of
is obtained using any of the three models. Xu and Froment kinetics [8] for both steam reforming
 187

TABLE 4. Bulk conditions for the single catalyst pellet in metha- used for the single catalyst pellet for steam reforming of
nation reactions at a pressure of 2050 kPa methane (Table 1) are also adopted for the methana-
tion reactions. The process of methanation is exother-
Gas composition Mole fraction
mic but the reactions do not contribute to a rise in
co 0.00350 temperature along the length of the methanator greater
CO2 0.00098 than 60 K [25], therefore a practical temperature range
H* 0.93550 (573-653 K) is covered in this study.
CH, 0.04399
Hz0 0.01600
Effectiveness factors
The effectiveness factor profiles for reactions I a&
III resulting from the dusty gas and simplified models I
and methanation reactions allows the implementation and II are shown in Fig. 5(a) and that of reaction II is
of this kinetics for investigation of the behavior of the presented in a separate Figure because its profile shows
single catalyst pellet for methanation reactions. The a different behavior. The effectiveness factors of reac-
rigorous dusty gas model as well as simplified models I tions 1 and TIT decrease with the increase in the temper-
and II are used to carry out this investigation. Feed ature. Reaction III has effectiveness factor values
conditions of an existing Saudi methanator are taken as greater than unity at low temperatures.
the bulk conditions for the single catalyst pellet and are Figures 5(b) and (c) present the effectiveness factor
summarized in Table 4. The same catalyst parameters and the intrinsic and actual rate of reaction profiles of

2 0.0012
REACTION 111 - DUSTY GAS MOOEL
! O.OO~O_ --- SIMPLIFIED MODEL I
m ___-__ SIMPLIFIED MODEL II /
t_ o.ooost
WSCTION I1
: 0.0006 l- /
REACTION I

--__
-.I ..
I - WSTY GA5 MODEL
- --- SIMPLIFIED MODEL I
______ SIMPLIFIED MODEL II

TEMPERATURE (K ) TEMPERATURE (K)

- UJSTY GA!5 MODEL

--- SIMPLIFIED MODEL I
______ SIMPLIFIED MODEL II
IIF
REACTION
11
I

573 593 613 633 653 573 613 635

(b) TEMPERATURE (HI Cd) TEMPERATURE (K)

Fig. 5. For the dusty gas model and simplified models I and II: (a) effectiveness factor profiles of methanation reactions I and III; (b)
effectiveness factor profiles of methanation reactions II and III; (c) effect of temperature on the intrinsic and actual rates of methanation
reaction II; (d) effectiveness factor profiles of CO, CO,, H,, CH,, and H,O for methanation reactions.
188

reaction II obtained by the dusty gas and simplified based on individual reactions can only occur based
models I and II. The effectiveness factor profiles show upon the net rate of reversible reactions (they cannot
erratic behavior and negative values. The intrinsic and occur for single irreversible reactions), which means
actual rates of reaction profiles show that this erratic that diffusional limitations reverse the direction of the
behavior and the negative effectiveness factors can be net rate of the reversible reaction. The same kinetics
explained on the same basis as for the steam reforming was used to investigate the methanation reactions
case. (which are the reverse of the methane steam reforming).
The effectiveness factors of the components are This part of the investigation has shown that the results
shown in Fig. S(d). The effectiveness factor profiles of of the simplified models always deviate from those of
CO, show similar behavior to the effectiveness factor the dusty gas model, which means that the nonrigorous
profiles of reaction III (Fig. 5(a)) while the effectiveness simplified models cannot be used accurately to predict
factor profiles of the other components (CO, H,, CH,, the behavior of this system. The erratic behavior and
H,O) show similar behavior to reaction I. The effective- negative effectiveness factors have also been observed
ness factor profiles of the components CO, H,, CH,, for the methanation reactions.
and H,O are very close to each other and can be de-
scribed by a single effectiveness factor profile as a good
approximation. Nomenclature
The effectiveness factor profiles obtained by the dusty
total molar concentration, kmol/m3
gas model for the reactions and the components show
molar concentration of component i,
large deviations from those obtained by the simplified
kmol/m3
models I and II.
characteristic diffusional coefficient, m2/h
Knudsen diffusivity of component i, m2/h
molecular diffusivity for component i in
Conclusions
binary mixture of i and j, m*/h
effective molecular diffusivity for compo-
The steam reforming of methane under industrial
nent i in binary mixture of i and j, m2/h
conditions is characterized by high diffusional limita-
effective diffusivity of component i, m*/h
tions, that is, the reactions are completed in a thin shell molecular diffusivity of component i in
near the surface of the catalyst pellet and the tempera- multicomponent mixture, m2/h
ture has a pronounced effect on the reactions. At low effective molecular diffusivity of compo-
steam to methane ratios the predictions of the three nent i in multicomponent mixture, m2/h
models are in good agreement; however, at high steam heat of reaction, kJ/mol
to methane ratios the simplified models show a large reaction rate constants of reactions I and
deviation from the dusty gas model. This implies that at III, kmol kPa0.5/kg h
low steam to methane ratios the simplified models, reaction rate constant of reaction II,
although not rigorous, are adequate for simulating this kmol kPaa/kg h
system, while at high steam to methane ratios the equilibrium constant of reaction I, kPa*
implementation of the dusty gas model is essential for equilibrium constant of reaction II
the accurate prediction of the behavior of such compli- adsorption constants for CO, H,, CH4,
cated gas-solid systems. and H,O, l/kPa
Erratic behavior of components and reaction effec- characteristic length of catalyst pellet, m
tiveness factors was obtained by the rigorous dusty gas molar flux of component i, kmol/m* h
model as well as the simplified models under different total pressure, kPa
conditions. All models predict the same phenomenon of partial pressure of component i, kPa
positive-negative fluctuations of the components and rate of reaction of component i, kmol/kg
reaction effectiveness factors at different conditions, cat. h
clearly showing that this is a true physical phenomenon rates of reactions I, II, and III, kmol/kg
and is neither a result of numerical artefacts nor a result cat. h
of certain simplifications of the diffusion reaction mod- dimensionless reaction rate of methane
els. Negative effectiveness factors for the components dimensionless reaction rate of steam
physically mean that for complex reaction networks universal gas constant, kJ/kmol K
diffusional limitations may reverse the direction of the external surface area of catalyst pellet, m2
net production or consumption of certain components temperature, K
compared with their direction in the absence of these volume of catalyst pellet, m2
diffusional limitations. Negative effectiveness factors mole fraction of component i
 189

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Pi ratio of Knudsen diffusion coefficient of (1989) 88.
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