MULTIPLE OXIDATION REACTIONS AND DIFFUSION IN

THE CATALYTIC LAYER OF MONOLITH REACTORS

KYRIACOS ZYGOURAKIS*
Department of Chemical Engineering,Rice University,Houston, TX 77251, U.S.A.

and

RUTHERFORD ARIS
Department of Chemical Engineeringand Materials Science, University of Minnesota, Minneapolis,
MN 55455, U.S.A.

Abstract-Oxidation reactions of mobile exhaust gas in a catalyticmonolith are considered in this paper.
The exhaustgas is deseribed by four concentrations, namely those of the carbon monoxide, fast- and
slow-oxidizing hydrocarbons and hydrogen. The problem of multiple reactions and diffusion in the
catalytic layer of the monolith walls is studied first. The diffusional resistance of the catalytic layer is often
significant in spite of its thinness and it seemsimportant to allow for both the hydrogen and hydrocarbon
oxidation reactions in analyzing the system for steady-state. The influence of hydrogenon the multiplicity
of steady-statewall temperaturesis also studiedand it is found to be important, because hydrogenreacts
rapidly at lower temperatures.

1. INTRODUCTION the member species. Kuo’s assumptions are sup-

The principal atmospheric pollutants present in
automobile exhau?t gas are carbon monoxide, a large
variety of hydrocarbon species and nitrogen oxides.
The exhaust gas, which contains also significant
amounts of hydrogen, is mixed with secondary air
injected in the exhaust pipe.. It is then passed through
the catalytic converter, where the c&bon tionoxide,
the hydrocarbons and the hydrogen are catalytically
oxidized [ 1, 23.
In this paper the problem of multiple reactions and
diffusion in the catalytic layer of monolithic reactors
is investigated. The question that arises naturally in
such complex nonlinear systems is whether there exist
multiple steady state solutions to the reaction-
diffusion problem[l4,251. The solution structure of
this pioblem is analyzed using a monotone iterations
method. The importance of the diffusional resistance
of the catalytic layer is also demonstrated.
Finally, the effect of hydrogen and hydrocarbon
oxidation on the steady state temperatures predicted
for a slab of monolithic catalyst is studied. The
implications of the present steady state analysis on
the performance of the monolith reactor are also
discussed.
2. DEVELOPMENT OF MATHEMATKXL MODEL
Because of the large number of hydiocarbcm spe-
cies found in the exhaust gases[l-31, it is impractical
to model the oxidation of each one separately. Kuo
et ~1.[l] proposed lumping the hydrocarbons into two
reactive groups, according to the ease with which they
are catalytically oxidized. Each group is then consid-
ered to be an independent entity with a separate
kinetic expression describing the reaction rate of all
*Author to whom correspondence should be addressed.
ported by several experimental investigations of the
catalytic oxidation kinetics of hydrocarbons[4-61.
Following this hunping scheme, we will consider
that the following four gaseous species react in an
oxidation catalytic converter:
(1) Carbon monoxide
(2) Fast-oxidizing hydrocarbon fraction (HCl),
which consists mainly of olefins, acetylene and
aromatics
(3) Slow-oxidizing hydrocarbon fraction (HC2),
which consists mainly of methane and ethane
(4) Hydrogen.
In the discussion to follow these reacting species
will bc designated by the subscripts 1 through 4 as
defined above, with the subscript 5 used for oxygen.
The reaction rate expressions for the oxidation of
mixtures of carbon monoxide, fast- and slow-
oxidizing hydrocarbons over a platinum-alumina
catalyst were obtained by Voltz ez al. [I and have the
form:
ri= -k,,YiY5/R’ i = 1, 2, 3 (1)
where Y, is the mole fraction of the ith component
and R’ is a resistance term accounting for the in-
hibition effects of carbon monoxide, fast-oxidizing
hydrocarbons (HC1) and nitrogen oxides, which is
given by:
R’ = [l + k,, Y, + kdY;]‘[l + k,,Y,zY~z]
x [1 + k,(NO)‘.‘J. (2)
The oxidation of hydrogen present in the exhaust
gas poses a more difficult problem. Although the
oxidation of Hz alone on platinum or supported

733
734 K. Z~cioua~~rs and R. ARIS

platinum catalysts have been studied extensively (see The boundary conditions (5) indicate that the
for example [S-lo]), there is but a limited amount of ceramic forming the monolith walls is assumed to be
kinetic data for the oxidation of H&O or impermeable to matter.
Hz-CO-hydrocarbon mixtures. We will assume in Equations (4&(6) become in dimensionless form:
this study that the reaction rate expression for the
oxidation of hydrogen is given by:
d’yi &?(I -_yXl -y,)RCy,,yJ
drz = -
(7)
r, = - k,Y,Y,fR’ (3)

where R’ is the resistance term defined by eqn (2). dyi

x=0 @5=0
This assumption is compatible with the experimental
observations of Hawthorn[l I] and Dabill et af.[12].
The numerical calculations that support the validity
of this assumption and the choice of the kinetic
constants in eqn (3) are presented in Appendix A.
For typical monolith designs, the ratio of the for all i = 1, 2, 3, 4 where:
thickness of the catalytic layer over the passage
hydraulic diameter is very small. We may assume,
therefore, that the catalytic layers have flat-plate ( = 7, yi = 3$ i= 1, 2, 3, 4, 5
geometry. Also, the Prater relation[l3] suggests that A
the temperature change in the catalytic layer is less
than l”C, for the reactant concentrations encoun- ,$+y, B,=$ k .I i= 1, 2, 3, 4.
tered in automobile applications. Thus, the catalytic ei Ei
layers may be considered to be isothermal.
In Fig. 1 the cross section of a square passage is The concentration of oxygen at the reactor inlet is
presented, showing the geometry of the system. adjusted to be significantly larger than the stoichio-
Under steady state conditions, the mass balance metric concentration needed for the full conversion of
equations for the reacting species in the catalytic layer the oxidizable species. Many investigators[lbl6]
and their boundary conditions become: have considered only the case in whidh oxygen is
present in very large excess. Then
Deis =KriYiY5R(Y,, Y,) i = 1,2,3,4 (4)
Ys N Y,, or y, = 0
dY,
-_=O @x=0 i= 1,2,3,4 (5)
dx throughout the catalytic layer and eqns (7) are
significantly simplified. Less restrictive assumptions
can be employed, however, to eliminate the need of
kJYbi-- YJ=D,z @x =I i=l,2,3,4 (6)
solving a fifth boundary value problem for the oxy-
gen concentration simultaneously with the problems
where
described by eqns (7)-(9). By using the fact that the
K,i = k,J[ 1 + k,(NO)“.7] concentrations of hydrocarbons are much smaller
than those of CO and H,, and that H, reacts much
and
faster than CO[l 1, 121, the mass balances for the O2
R(Y,, Yz)= l/(1 +k,,Y,+k.,Y,)*(l +k,,Y,‘Y,*). in the catalytic layer and the catalyst-gas interface.
yield:

l-_YY,=&--E,Y, (10)

where E. = 1 - 1.25YJ Y,, and E, = Yb,/(2Yb5). The

details leading to eqn (10) can be found in [Zl].
For typical monoliths the Reynolds numbers vary
between 25 and 400 and, therefore, the flow in the
straight parallel passages is laminar. The mass and
heat transfer coefficients were calculated using well-
known correlations proposed by Hawthorn11 1] and
Vortruba et al. [ 171. The necessary values of limiting
Nusselt numbers are given by Kays and London[l8]
substrate
for many passage geometries. The corresponding
limiting Sherwood numbers for each species were
computed using the heat and mass transfer
Fig. 1. Cross section of a square monolith passage.. analogy[l9].
 Multiple oxidation reactions and diffusion in the catalytic layer of monolith reactors 735

3. SOLUTION OF THE SYSTEM OF COUPLED BVPS The monotone iterations method is a successive
AND THE QUESTION OF MULTIPLICITY approximation scheme. Starting from an
The steady state problem of multiple reactions upper-upper solution 6+“,yz0) = (1, 1) as an initial
taking place in the catalytic layer requires the solu- approximation, we compute a sequence of iterates
tion of the system of boundary value problems (v,“, yr”) by successively solving linear and uncoupled
(BVPs) described by eqns (7HlO). Obviously, the BVPs of the form
two BVPs for the concentration of carbon monoxide
and fast-oxidizing hydrocarbons (i = 1, 2) are cou- d?,
pled and highly nonlinear, because of the term -@ - &Y: = -JXY,” - ‘9 Y,“_ ‘)
(E,, - E,yr)RoJ,, yr)_ Once this system is solved for __Q:-‘; j= 1,2
y,(l) and y,(c), the two remaining BVPs for the (14)
slow-oxidizing hydrocarbons and hydrogen become
dyl
-=O @r-O; i-l,2
linear in y,(r) and y4(t) respectively and can be easily (15)
solved. de
We now turn our attention to the system of
coupled and nonlinear BVPs: ~+a,;=0 f&r =I; i = 1,2. (16)

d’Yi
p = -n_Y,.Y2); i = 1, 2
dyi
-=O @t=O; i=l,2
d<
dyi
,g+g$;=o @i=l; i=l,2.
It was first attempted to solve this system using a
global collocation scheme. Newton-Raphson’s and
Powell’s method[20] were used to solve the resulting
system of nonlinear algebraic equations. However,
significant numerical difficulties were encountered
(see[21-231 for a detailed discussion). The nonlinear
iterations diverged even for moderate temperatures
(80&900”K) and the accuracy of the approximations
to the profiles y,(c) and y*(c) deteriorated rapidly
with increasing temperature, to the point that they
would become unacceptable for the solution of the
BVP which would yield the hydrogen profile.
The major drawback of the nonlinear iteration
methods, however, lies in the fact that they do not
answer the question of multiplicity of steady-state
solutions. We should note here that the question of
multiplicity has not been answered convincingly even
in the case when a single reaction (CO oxidation) was
considered to take place in the catalytic layer of
monolith reactors[l4,25] (see also [16] and [24]).
The multiplicity question is all the harder to answer
when multiple reactions are taking place in the
catalytic layer. The use of a searching technique in
conjunction with nonlinear iterations would require
prohibitively long computation times. For all these
reasons, the monotone iterations scheme with adap-
tive collocation developed in companion
publications[22,23] was used to solve this system of
coupled BVPs. This method provides a priori unique-
ness criteria as well as a multiplicity criterion, that
can be numerically implemented. In addition, it pro-
vides guaranteed convergence for all values of Thiele
moduli and computes the solutions with very high
accuracy by using an adaptive collocation
scheme 1231.
(11) It has been shown [22] that this sequence of approx-
imations decreases uniformly in the interval [0, l] and
monotonically until it converges to the maximal
(12) solution (y:, y_$) of the system. Another sequence of
iterates (w,“. wz”) can be generated starting from
(w,O, wrO)= (0,O) as an initial approximation and
(13) solving successively the BVPs defmed by eqns
(14)-(16). The latter sequence increases uniformly
and monotonically until it converges to the minimal
solution (*y,, eyr). If now (JQ,yr) is any other solution
of the system (llH13), then
cyiIy,Iy:; i = 1,2 for all c in [0, 11. (17)
Therefore, if the computed maximal and minimal
solutions are identical, the BVP system (llH13)
has a unique solution. If they are not identical, then
the problem has at least two positive solutions and
any other solution will be bounded by these two. The
high accuracy of our numerical algorithm[23] makes
such a determination possible.
The nonlinearitiesf,(y,, y2) andf,(y,. y2) in eqn (11)
have been studied in detail[21]. We have found that,
for all values of temperatures and concentrations in
the range of practical interest, they satisfy the
conditions
%>-A. i=1,2 (18)
ay, ”
a
-s-O; i#j, i,j = 1,2 (19)
8Y,
for all values of y,, yr, where A,, A, are sutliciently
large positive constants. Thus, the convergence of the
nonlinear iterations defined by eqns (14H16) is al-
ways guaranteed, according to the results presented
in [22].
The monotone iterations method is indeed a pow-
erful tool and has enabled us to investigate the
problem of solution multiplicity. The following range
of parameters was completely characterized:
T = 500-1200X, Y,, = O-0.06, Ybz= O-2000 ppm.
736 K. ZY~~UIUKISand R. Aars

It has been assumed that the oxygen bulk concen-

tration was gwen by Yb5= E + fYb,,with E =0.02
and 0.04[1].
No multiple solutions were computed in the above
range of parameters. In all cases, both sequences of
iterates “pinched’ the same final solution, converging
to it from above and below respectively. The in- 1.2.

vestigation of the solution structure was facilitated in

certain ranges of parameter vahres by using the a
priori uniqueness criteria presented in [22] and the ?I
fact that the monotone iterations provide uniform
upper and lower bounds to the solutions that become
.a
sharper at every step[21]. No indication of multiple
solutions was observed in several runs with reactant
bulk concentrations outside the previously mentioned
ranges.
We conclude, therefore, that the BVP system
(12)-(14) does not exhibit multiple steady-state solu-
.4
tions for the parameter range of interest in auto-
mobile applications.

4. DIFFUSIONAL RESISTANCE AND THE EFFECXS

0. a01 0.02 0.03 0.04
OF HYDROCARBON OXIDATION
Y
bl
The numerical results show that the thin catalytic
layers of commercial monoliths will present Fig. 3. The effect of HCl bulk concentration on the
significant diffusional resistance even at moderately effectivenessfactors for CO oxidation.
high temperatures. This effect has often been ne-
glected in monolith calculations ([15,2q). Figure 2
shows the computed effectiveness factors for CO and Figure 3 shows that the effectiveness factors for the
HCl oxidation at different temperatures as a function CO oxidation depend strongly on the bulk concen-
of Yb,. Even at 625°K the effectiveness factors have tration Yb2of the fast oxidizing hydrocarbons. Larger
values much smaller than unity for low concen- values of Y,,zresult in higher effectiveness factors and
trations of CO. At all temperatures, however, the shift the maximum of the curves towards smaller
effectiveness factors rise sharply as Y,, increases and values of Yb,_ This behavior is expected because the
may reach values significantly larger than unity. reactions follow negative order kinetics in both CO
and HCl.
The computed apparent rates for the CO oxidation
are shown in Fig. 4 for different bulk concentrations
of HCl. Clearly the hydrocarbons exhibit strong
I.2 inhibition effects and even small concentrations (e.g.
400 ppm) can significantly lower the oxidation rate of
CO and decrease its overall conversion in a catalytic
reactor.
qi
When the temperature of the catalytic layer in-
creases, the CO effectiveness factors exhibit the
.a behavior shown in Fig. 5. Higher temperatures shift
/ the curves to the right, while the maximum values
become larger and occur at higher Yb,. Finally at
about 700°K the maxima move out of the in-
vestigated region of CO bulk concentrations between
0 and 0.06 mole fraction. At higher temperatures the
CO effectiveness factors increase. monotonically in
the above range of Yb,.
It is interesting to note that at high temperatures
the dependence of the apparent rate of CO oxidation
on Y,, seems to bc. of positive order. This is illustrated
_-
._______-- in Fig. 6. For temperatures less than 650°K the
.C
0!02 O!OJ 0
apparent rate is clearly negative order dependent on
Y Yb, But at 675OK, the apparent rate increases mono-
bl
Fig. 2. Effectivenessfactors (- CO oxidation -- HCI tonically with Yb, up to 0.04. That can be. misleading,
oxidation). since for this temperature and HCI bulk conccn-
 Multiple oxidation reactions and ditTus.ionin the catalytic layer of monolith reactors 737

10-l

:1 :1

--_
102 lc+

1
J

Yb2’ 400 ppwl

T I 625 OK

A
-3
10
z 001 0.02
Y
bl
0.03 0.04 la36
0
Ybl
0.04

Fig. 4. The effect of HCl bulk concentration on the Fig. 4. The effect of temperature on the apparent rate of
apparent rate of reaction i, for CO (including diffusional reaction ;, for CO (including diffusional limitations).
limitations) -- Interphase mass transfer limited rate.

tration, the CO oxidation apparent rate reaches its
maximum at about Yb, = 0.05 and then starts de-
creasing, in accordance with the negative order kinet-
ics of the reaction.
Although the rates of both reactions are very fast,
the reactions do not reach the intraphase diffusion
control regime even at 9OO”K, as Fig. 7 shows. At this
temperature the qssumption of intraphase diffusion
control introduces an error in the computation of the
apparent reaction rate i, that can be as high as 10%
for Y,, = 0.04 and Y, = IOOOppm. We note, how-
ever, that at these high temperatures the hydro-
carbons exhibit negligible inhibition effects. The ex-
planation is presented in Fig. 8, where the

100 _

T q SO0 OK

1.2

Ti

.8 tt /
lf //
//’ / ,/ /
/ / /
Yb2-. 400 ppm
I

// / / / / /’
4

/
0.01 0.02 0.03 0.04 0.05
Ybl ’ bl

Fig. 5 Effectiveness factors for CO (-_) and I-ICI (- - -) Fig. 7. Apparent rate of reaction i, for CO - high tem-
oxidation-the effect of temperature. perature case. -- interphase mass transfer limited rate.
 K. Z~ooua~~rs and R. Ams

lysts with bimodal pore size distributions like the one

T ~900 ‘=K
used here.
Ybf0.04
The concentration profiles of hydrogen and slow
Y b2=
oxidizing hydrocarbons can be computed once the
400 ppm
profiles of carbon monoxide and fast oxidizing hy-
drocarbons are known. Since the hydrocarbon frac-
.OB- tion HC2 reacts very slowly, its concentration re-
mains almost constant in the catalytic layer even at
y; temperatures above 1000°K.
‘bi Hydrogen, on the other hand, reacts at a very fast
rate. At all temperatures where significant reaction
occurs, the reduced concentration of hydrogen Y,/ Y,
.04-
is much smaller than that of carbon monoxide
through the catalytic layer. Since Y,, 2 3 Y, under all
conditions [ 1,2], the hydrogen contributes very little
to the depletion of oxygen in the catalytic layer.
Therefore, the assumption made in Section 2 for the
computation of Ys should introduce very little error
*
in the computation of the CO and HCl profiles.
Computed concentration profiles for carbon monox-
Fig. 8. Concentration profiles of CO and HCl in the ide, fast oxidizing hydrocarbons and hydrogen are
catalytic layer-high temperature case. shown in Fig. 9.

concentration profiles of CO and HCl are plotted.
Since the hydrocarbons react much faster than the
CO at this temperature, their dimensionless surface
concentration is almost 2.5 times smaller than that of
CO and drops quickly to zero as the reaction pro-
ceeds in the catalytic layer.
In all the above computations we have considered
a comercially available catalyst with an alumina
support. The physical properties of the support were
given by Hegedus et aZ.[24]. The elfective diffusivities
of the reacting species in the catalytic layer were
computed according to the random pore model of
Wakao and Smith[l3], which is applicable to cata-
T ~700 OK
Yb,Z 0.02
Yb2Z 400 ppm
.2
yi
‘bi
.6
Fig. 9. Concentration profiles of CO, HCl
catalytic
5. STEADY-STATE TEMPERATURES FOR THE
MONOLlTH WALLS
In the previous section we have shown that the
hydrocarbon content of exhaust gases affects
significantly the rate of oxidation of carbon monox-
ide. Also, the heats of combustion of the hydro-
carbons have very large values (4195 kJ/gmol for
hexane vs 283 kJ/gmol for carbon monoxide). There-
fore even very low concentrations of hydrocarbons
can contribute a great deal to the heat generated in
the reactor. Many investigators[2], [27] have also
suggested that if the exhaust gas contains much
hydrogen, then the maximum wall temperature may
bc much higher than the equilibrium adiabatic flame
temperature of the gas. Hegedus[27] has actually
measured temperatures higher than the adiabatic one
during the oxidation of H, in a single passage mono-
lith reactor.
Our objective here will be to determine the effect of
the hydrogen and hydrocarbon oxidation reactions
on the steady state temperatures predicted for the
monolith walls. We will consider a thin slab of
/ ceramic substrate, coated on both sides by a thin
/ layer of platinum supported catalyst and exposed to
two streams of exhaust gas. Four gaseous species
oxidize within the catalytic layer: carbon monoxide,
hydrogen and fast- and slow-oxidizing hydrocarbons
(fractions HCl and HC2 respectively). The two gas
streams may have different bulk temperatures and
compositions.
Since the catalytic layers are very thin when com-
pared to the monolith walls, we will assume that the
reactions are actually taking place on the wall-gas
.8 interface. The geometry of the system is shown in Fig.
t 10.
and H, in the If we neglect axial conduction, the overall heat
layer. balance equation for the slab becomes
 Multiple oxidation reactions and diffusion in the catalytic layer of monolith reactors 739

The steady state solution of (23) is

W =w.+(w,-wJ[. (26)

Using (26) the boundary conditions are reduced to

CERAMIC I
SUBSTRATE I
I

Finally qns (27) and (28) yield

Cl-_ -----___ t
I
L--y2 % = zL(w‘J (29)

Fig. 10. Longitudinalsection of monolith wall. w, = I&(%) (30)

where

pcp$k$ O<x<L,,t>O (20)

and gb(wb) is given by eqn (31) substituting b for a.

with boundary conditions Two curves can now be obtained if cqn (29) is used
to calculate W, in terms of W, and eqn (30) to calculate
+-h.(T--J+k (-Aw,);,=O x=0(21) W, in terms of w,. Clearly the intersections of these
1=1 two curves correspond to the steady state solutions of
(23) subject to the boundary conditions (24) and (25).
-kg-h,(T-TT,)+ k (-AH,);,=0 x = L, (22) For all values of the dimensionless groups consid-
i-l ered in our system the two curves had always three
intersections on the diagonal line W, = w,, when the
where T, and Tb are the bulk temperatures of the two bulk temperatures and reactant concentrations of the
streams, h, and hb the heat transfer coefficients for the two streams were the same. By using the theorems
two sides of the slab, - AH, the heat of reaction and that Aronson and Peletier[29] have developed for the
i, the apparent rate of the ith reaction for the global stability of symmetric and asymmetric profiles
conditions at the appropriate side of the slab. in catalyst particles, it is immediately deduced that
The dimensionless variables are defined as the middle steady state is unstable. The lower and
upper steady states are stable, corresponding to the
T kf unignited and ignited states of the particle re-
w=- t=y
TO PCpL, spectively.
In order to establish the significance of hydrogen
where To is some reference temperature. Let also and hydrocarbon oxidation, the steady state wall
temperatures were computed using three different
B.,hC,
b
models:
k (I) Only the oxidation of CO was modelled. This
is the assumption used by most investigators
(see[l5,25,26]).
(II) Only the oxidation of CO was modelled and
the effect of hydrogen was accounted for by assuming
where i stands for a or b. that the heat of reaction for CO is given by
Then eqns (20)-(22) become
AHE = AH,, + $AHH2. (32)

This relation was first proposed by Kuo[l]. The

implicit assumption is that the oxidation rate of H,
is the same as that for CO and hence the ratio of H,
to CO in the reactor is 1: 3 everywhere.
(III) Oxidation for all four species was modelled
according to the assumptions discussed in Sections 1
and 2.
 K. ZV~~URAKIS and R. ARES

Table 1. Data for mmputations

A B c D
(CO), mole 0.04 0.04 0.025 0.01
fraction
(Ha), ppm 400 lOOD 200 200
(HCZ), mm 100 250 50 50
(H 1, mole 0.013 0.013 0.0085 0.004
?r action

(NO), wrn 60 60 60 2000

0, kg/h2)(s) 0.75 0.75 0.75 14.0

Driving mode DEXS31. DW331. Idling Accel.

The computations were done for four groups of
data, thought to represent typical conditions and
compositions of exhaust gas for different driving
modes of the automobile. These data are given in
Table 1. In the basic case considered, the values of
heat transfer coefficients were computed from the
limiting Nusselt number for flow between parallel
plates. Computations were also carried out for
different passage geometries. The formulas proposed
by Hawthorn[ll] were used for the calculation of
heat and mass transfer coefficients. The apparent
reaction rates ii were computed according to the
method discussed in Section 3.
The results of the computations are shown in Figs.
11 to 13, where the predicted wall steady state
temperatures are plotted vs the bulk temperature of
the gas streams.
In Fig. 11 the steady state temperature predictions
of Models (I), (II) and (III) are compared for data
group A. Model (I) predicts a single steady state over
the entire temperature range considered. Model (II)
predicts ignition’ at about 600°K and after a very
narrow and sharp multiplicity region the wall tem-
perature jumps to high values.
Model (III) predicts three unmistakable steady
states for bulk temperatures between 420 and 580°K.
The steady states are widely spaced and an analysis
showed that they are not due to numerical errors.
When the bulk temperatures increase, the model
predicts ignition at about 580°K. The wall tem-
peratures attain very high values afterwards, which
exceed significantIy the adiabatic reaction tem-
peratures predicted for the given concentrations of
reactants.

1400-
DATA3 A

r
400 600 aoc
Tf [“K]
400 800
Tf,*K Fig. 12. Model III steady state temperature predictions for
various automobile driving modes (A -Deceleration, lou
Fig. 11. Wall steady state temperatures T predicted by hydrocacban concentration, E-Deceleration, high hydra
Models I, II and III vs bulk fluid temperature T/. carbon concentration, C-Idling, D-Acceleration).
 Multiple oxidation reactions and diffusion in the catalytic layer of monolith reactors
Fig. 13. Effect of mass flow rate and channel geometry on
Model III steady state temperature predictions.
This behavior is due to the presence of hydrogen.
As we have already noted (see also Appendix A),
hydrogen exhibits significant rates of reaction at
lower temperatures than those required for carbon
monoxide and thus causes ignition to happen at
lower temperatures. Also, since the Lewis number for
H, is 2.4 as compared to less than unity for CO, the
simple arguments presented by Wei[2] and
Hegedus[27] show that the walls can reach tem-
peratures higher than the adiabatic one.
The stability analysis shows that the solutions lying
on the middle branch between points E and G on Fig.
11 are unstable and hence physically unreahzable.
These results show that if the gas temperatures
increase slowly from the lowest values to the highest
and then decrease again, the wall temperature will go
through a classical hysteresis loop.
The effect of hydrocarbon concentration on the
steady state wall temperatures is shown in Fig. 12. A
comparison between the curves for data groups A
and B shows that even small concentrations can
increase the predicted wall temperature, due to the
large heat of reaction for hydrocarbon oxidation. For
larger hydrocarbon concentrations, however, ignition
will occur at higher temperatures because of the
inhibition effects of the HCl fraction.
In Fig. 12 the predictions for the other groups of
data are also given, showing the combined effects of
reactant concentrations and mass flow rates. As the
concentrations of reactants decrease, the multiplicity
region is shifted towards higher temperatures and
shrinks in size. Finally for data group D on different catalytic systems than the one considered
(Acceleration-lowest concentrations and highest
flow rate) the multiplicity region disappears com-
pletely.
CES Vol. 38. No. 5-F
741
In Fig. 13 the effects of mass flow rate and channel
geometry are briefly examined. When the concen-
trations of group A are used with the highest flow rate
(G = 14 kg/(mr)(s)) the multiplicity region becomes
smaller and is shifted to higher temperatures.
Considering that our assumptions are valid for a
square passage monolith, the model was tested by
assigning the Nusselt number to the appropriate
value for that passage geometry. The model predicts
that the multiplicity region will become wider and be
shifted towards lower bulk temperatures. Therefore,
ignition will occur earlier than in the case of the
parallel plate channels.
We should note here that if higher concentrations
of CO than those presented in Table 1 are used,
model (II) predicts multiplicity regions that are wide
enough to be computed accurately. In ail cases,
however, model (III) predicted wider multiplicity
regions, with slightly lower ignition temperatures and
significantly lower extinction temperatures than those
found by model (II).
Hegedus et al. [24] have studied the multiple steady
states in an isothermal reactor for the oxidation of
CO over platinum-alumina. They have computed
and observed experimentally inlet temperature-
conversion hysteresis for CO inlet concentrations in
the range of 0.003-0.005. They observed, however,
that tbe Voltz er ai.[7] kinetic model would predict
multiplicities only at very high CO concentrations.
They claimed that this different behavior was caused
by the water vapor content of the gas streams used
in Voltz’s experiments (while theirs were conducted
with dry feed streams) and verified this assertion
experimentally. These observations support our
finding that model (II) predicts multiplicities for
carbon monoxide concentrations higher than 0.04.
Multiple steady states have also been observed
experimentally by Vortruba and Hlavacek[ZS] for the
oxidation of CO in honeycomb monolithic reactors.
The observations have the form of inlet temperature-
conversion hysteresis loops. Very sharp changes were
observed as the reaction ignited or became extinct,
with the conversion jumping from almost zero to
almost unity or vice versa at the ignition or extinction
temperatures. Multiplicities were observed for CO
concentrations in the region of 0.04-0.06, while one
steady state was found for low concentrations of CO.
Higher concentrations of CO decrease significantly
the extinction temperature and increase slightly the
ignition temperature. Tbe same qualitative conclu-
sions may be drawn from the results presented in Fig.
12 (curves A and C which correspond to different
reactant concentrations). Vortruba and Hlavacek
also observed that the multiple steady states disap-
pear for high Reynolds numbers. The same behavior
is predicted by our model (see curve D in Fig. 12).
The above mentioned experiments were performed
in our study.
We conclude that both the hydrogen and hydro-
carbon oxidation reactions have a significant effect
142 K. ZYG~URAKIS and R. ARls

on the steady states wall temperatures and should be REFERENCES

included in monolith calculations. The effect of hy-
drogen is especially important since it was found that
it can significantly enlarge the multiplicity region by
lowering dramatically the extinction temperature. It
also results in higher wall temperatures than those
predicted by considering only the CO oxidation.
When the oxidation of hydrocarbons is also consid-
ered, the wall temperature obtains still higher values
and the ignition temperature increases.
NOTATION
mass transfer Biot number for component i,
k&ID,
heat transfer Biot number, h,L,/k
mass heat capacity of solid, J/kg”K
effective diffusivity of component i, m2/s
constants defined by eqn (10)
nonlinear functions of y, and y2 defined by
eqn (7)
functions defined by eqn (31)
mass flow rate, kg/(m*)(s)
heat transfer coefficient, J/sm*“K
thermal conductivity of solid, J/sm”K
mass transfer coefficient for component i, m/s
thickness of catalytic layer, m
thickness of monolith wall, m
apparent rate of reaction i, gmol/sm*
time, s
temperature, “K
dimensionless solid temperature, T/T,
length coordinate, m
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Auromo~iue Engrs. 1971, Paper No. 71-0289.
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[20] Powell M. J. D., In Numerical Methods fir Nonlinear
Algebraic Eyuations, (edited by P. Rabinowitz), p. 115.
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dimensionless concentration of component i [22] Zygourakis K. and Aris R., J. Nonlinear Analysis:
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[24] Hegedus L. L., Oh S. H. and Baron K., A.I.Ch:E:J.
Greek symbols 19-c 23 632.
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[26] Heck R. H., Wei J. and Katzer J. R., A.I.Ch.E.J. 1976
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59.
or b
[29] Aronson D. G. and P&tier L. A., Arch. Ration. iUech.
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solid density, kg/m3 Scientific Znstr. 1975 8 37.
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[32] FisherG. B. and Gland J. L., General Motors Research
Thiele moduli, &I2 Y,,/D,i Publication GMR-2944R. PCP-92R.

Subscripts and superscripts APPENDIX A

bulk value The catniytic oxidation of hydrogen

fluid value
Hawthorn[l I] presented a limited set of industrial data
iteration number for the oxidation reactions of CO, H, and hydrocarbons on
reference value platinum alumina catalysts. These data show that the
CO, CO oxidation catalyst is most active for hydrogen oxidation, with
sienificant reaction startine at 325°K and hi& conversions
HCl, HCl oxidation
at- temperatures higher &an 420°K. Compared to that,
HC2, HC2 oxidation carbon monoxide shows significant reaction at 445°K with
H,, H, oxidation high conversions obtained above 570°K. Dabill et al.[lZ]
02 observed that in the presence of CO, the oxidation rate of
 Multiple oxidation reactions and difhusion in the catalytic layer of monolith reactors

hydrogen is inhibited by CO to approximately the same

extent as the oxidation of CO itself.
In accordance with these observations, the following
expressions were used throughout this study to predict the
rate of reaction for H,:
6
~“2 = - k,@I,)(CO)IR’

k, = k,exp [E*/Rr]k,,

where R’ is the resistance term defmed in Section 2 and k,, Qr

is the kinetic constant for CO oxidation[7]. The numerical
calculations supporting the validity of these expressions and 4
our choice of the constants k, and E* are now presented.
The catalytic oxidation of H&O mixtures over platinum
was investigated. The reactions take place in the catalytic
layer of a monolith wall, which is exposed to a flowing
stream of air containing small concentrations of the reac-
tants. The following kinetic expressions were assumed
L
- rco = k,,(CO)(O,)IR (A)

- r,, = k, exp LWR~lk,(~,W,~IR @I

where

R = (1 + k,,(C0))2 (C) C

The constants k,, and k,, were taken from the kinetic 460 560
T OK
model proposed by Voltz et a1.[7]. The effectiveness factors
for the two reactions were considered to be equal to unity, Fig. Al. Heat released during the oxidation of Hz-CO
and the catalytic layer was assumed to be isothermal. Then mixtures over supported platinum catalyst for k. = 1.1 and
simple mass balances for the two reactants yield
E* = 1600°K. (- * (Hz) = 0.005, (CO) = 0; - (H3 = 0.01,
(CO) = 0.005; -- (H,) = 0.005, (CO) = 0.01; -.- (H2) = 0,
kp,( Y,. - Y,) = lr,, @) (CO) = 0.01).
where i stands for CO or H,, Y, and Y,, are the respective
bulk and surface concentrations of the two reactants and r,;
are the reaction rates expressed per volume of catalyst.
The system of nonlinear algebraic equations (D) is solved
to give the surface concentrations of the reactants. In order
to compare. our results to those of Dabill et al. [12], we have
computed the total heat generated by the two reactions as

Qr = (- AH&., + ( - AH&,,. (E) 6

In the experiments discussed by Dabill er al. the rate of

reaction was monitored as the change in electrical power
required to maintain the platinum catalytic wire at constant
temperature. This change is directly proportional to QT
QT
given by eqn (E) (see [30]).
The numerical simulation results are presented in Fig. Al, 4
where Q, is plotted vs the temperature of the catalytic
layers. The values of the parameters used in this case are
k,= 1.1 and E*= 1600°K.
The results are strichingly similar to those presented by
Dabill et al. When only hydrogen is oxidized, the reaction
starts at 360°K. The oxidation of CO starts at about 470°K.
Both temperatures agree well with the values Dabill has 2
measured, with that for hydrogen higher by 3040°K. The
oxidation of Hz-CO mixtures follows the same behavior
observed in Dabill’s experiments. The oxidation of hydro-
gen is inhibited by the presence of CO as eqn (B) suggests.
Then the oxidation of the H&O mixture starts at some
intermediate temperature between those for H, and CO
alone and the rate of reaction rises very sharply to become
diffusion limited. The minimum oxidation temperatures
400 :
predicted for the different ratios of H&O in the mixture T , OK
agree remarkably wet1 with those measured by Dabill.
We conclude that the simple model used in this study Fig. A2. The effect of parameters k,, and E* on the ox-
captures the essential features of the oxidation of H&O idation rate of H,. (- k. = 5.5, Ef = 2tlOf~“K; + -
mixtures discussed bv Dabill ef al. The above values of k, k,=l.l, E*=20iWK; - k,=l.l, E*=,mOK; __
and E* have been u&d in our numerical simulations. Thk k, = 1.1, E* = 1200°K).
744 K. ZYGOURAKISand R. Ams

effect of the parameters on the oxidation of hydrogen is
shown in Fig. AZ. We should note that the minimum
oxidation temperature of hydrogen does not depend
strongly on the values of k. pnd E*.
The possible inhibition e.Rects of water vapor on the
oxidation of hydrogen on platimm[31] are not accounted
for by our simple model. Experimental invcstigations[32]
have shown that water adsorbs on platinum less strongly
than carbon monoxide. One would expect therefore that CO
is a much stronger inhibitor of these reactions than H,O.
The validity of this assumption, however, should be checked
exDerimentally.