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Shorter Communications 491

(c) For flow of single fluids in packed beds the dispersion the dispersion models should hold with
model should hold well, however, for the non-coalescing dis-
persed phase of-two phase systems the convective mode1 should
be used because difTerent sized particles or droplets move at
dierent mean velocities. What of the intermediate situation of a few coalescences only?
(d) To see which model better fits a particular flow situation Should we develop a flow model in which
we must ask Do the elements of lluld experience a constant
reshuftling of their identities, or do some elements always move IT2= L, l~flS2
faster, others always slower?
(e) In recent years there has been mounting interest in flow where n characterizes the location between these extremes? Or
characterization of multiphase systems such as trickle beds, should we use some other measure? This is an interesting ques-
bubble columns, spsry columns, and so on. A recent compre- tion which we leave for others.
hensive Journal Review by Shah et al. (1978) lists hundreds of
studies in this area. But what is pertinent is the continual Acknowledgement-The authors would like to acknowledge their
reference throughout this review to the Gaussian dispersion gratitude to Prof. E. N. Lightfoot for his helpful comments.
model and other stochastic type models to represent these Bow
systems. And what is remarkable is that, ss far as can be seen, Chemical Engineering Department OCTAVE LEVENSPIEL*
not one of these hundreds of studies ever considered using a Oregon State Unioersity T. J. FITZGERALDt
convection type model! Corvollis, OR 97331, U.S.A.
(f) So far we have only mentioned one-dimensional flow situ-
ations. However, the sane considerations apply to multidimen-
NOTATION
sional flows. For example, in the air pollution literature and also
for liquid jets it is common practice to use Gaussian dispersion D axial dispersion coefficient, m2/s
expressions for the spread of material from a point source. With E, the RTD or exit age distribution function, s-
such a model one usually iinds dispersion coefficients which are Es the RTD in dimensionless time units
not constant, but vary with distance from the source, indicating L length of vessel or section of vessel, m
that this model is inappropriate for these situations. It may well RTD the residence time distribution
be that a convection type model should be used, at least for the t time, s
spread of material io one of the directions. t =& mean residence time, s
(g) Let us return to our falling droplet example, the bigger u
ones falling faster, the smaller ones falling slower, the RTD I( linear velocity of fluid, m/s
Gaussian. With no coalescence the Convective-Gaussian model
should hold with Greek symbols
0 = 4 dimensionless time
I
ut standard deviation of RTD curve, s
On the other hand with frequent coalescences of drop breakup ~0 standard deviation of RTD curve measured in terms of 0.
Also the flow parameter of the convective-Gaussian
model

*Author to whom correspondence should be addressed. REFERENCE


tPresent address: TRW Inc., Redondo Beach, California, Shah Y. T., Stiegel G. Y. and Sharma M. M., A.1.Ch.E. J. IV78 24
U.S.A. 369.

Chemical Enrbuering Science Vol. 3S, No. 3, pp. 491-493, 1983


Printed in Great Britain

A case of negative apparent activation energy due to pore diffusion effects

(Received 18 March 1982; accepted 23 JUry 1982)

In a 1976 review paper, Rajadhyaksba and Doraiswamy [ l] and C will be


considered various sources of falsification of apparent ex-
perimental kinetic parameters. One section treats the cases (De). k,C,
of parallel first order reactions in the asymptotic region of (3)
r&l= R(k, + k,)O.J
pore diffusion control (effectiveness factor < 0.5):
(De;O k2CA
(4)
r==R,(k,+k#-s

for the case k, % k,


As the disappearance of A is given by the sum of the two
rates, k, + kz, the effectiveness factor rl in the asymptotic rc = (De).Sk&, -%,/R, (5)
region is expected to be
Assuming that k, and k, can be expressed as Arrhenius
(De). 1 equations, the activation energy for (5) will be E2 - E, /2.
- R, (k, + k,)O,
(2) Thus, if El is more than twice as large as E+, we have the
unusual case of an apparent activation energy changing
where De is an effective pore diffusion constant, and R, is sign. due to pore diffusion falsification, in the case of
the radius of a catalyst Pellet. The rates of formation of B parallel, competing reactions.
492 Shorter Communications

We believe to have discovered such a case, although the is either a power law or is of the Langmuir-Hinshelwood
kinetics of the two competing reactions are considerably form.
more complex than those of (l), ruling out an analytical The apparent kinetics thus determined will clearly be
derivation, such as quoted above. The case in point is the subject to possible falsification by pore diffusion effects. The
competitive oxidation of carbon monoxide by oxygen and next section presents the apparent kinetics for the system
nitric oxide, in the oxidizing regime (CO -z 2 x Or + NO) CGNU, in the oxidizing regime. The apparent activa-
over an automotive three-way catalyst (l-WC). Here the tion energy for the N&CO reaction, in the presence of
C&O, reaction is the dominant one in the concentration oxygen, is negative. Yet, in the absence of oxygen the
regime of interest, resulting in the necessity of assigning an N&CO reaction has a rate exuression which increases
apparent negative activation energy to the CO-NO reaction. monotonically with temperature.

RESULTS
EXPERIMENTAL
Using the modeling procedure described above, the fol-
The catalyst was a commercial (Engelhard Industries type lowing expressions were found to be quite satisfactory in
lPD).monolithic three-way catalyst with 310 channels per describing the ternary systems CC%Nu,, in the oxidizing
square inch, coated with a 10 wt/, y-alumina washcoat. and region. -
containing 20/.NiO, 0.6% CeOs. 0.1% Ft and 0.01% Rh. It For the reaction CO + 0.5 0, = CO,,
had been thermally aged at 780C for 16 hr. The experiments
were carried out under steady state flow conditions, in the d[CO] 2.00 x 1Orexp (- 4.44 x 104/RT)[CO][0,]-*n
temperature range of 37&593C, at a space velocity of about dr (1 + 3035[co])*
50,000 hr - for the CcrOr-NO system, and 930,000 hr - for
(6)
the CO-O, and the C-NO systems. The maximum inlet
concentrations of active gases were 2.5% CO, 2400 ppm NO, For the reaction CO + NO = CO, + 0.5 N,
and about 2%0,. The gases always contained 10% water
vapor, 12% CO,, and.20 ppm SO,, with nitrogen as the re-
--=WOI -- d[NOl
maining diluent. These conditions are considered typical of dt dt
automotive exhaust in the very general neighborhood of
stoichiometric conditions where a TWC would be used. The 2.67 x lo- 2exp(4.57 x l@/RT)[CO]llIO]-
=
steam was produced by pumping water at a controlled rate (1 + 7.5977 x 1o[oJ)o*=2
into a steam generator. The remaining gases were taken from (7)
tanks, and their flow was controlled by Matheson mass flow
controllers. The analytical instruments used are typical for [CO], WO] and [0,] represent concentrations in mole frac-
this kind of work and have been described many times[2]. tions, at the surface of the catalyst-containing washcoat.
Integral conversion data were obtained by measuring con- Rate expressions (6), (7), (7) and (8) represent fluxes into the
centrations before and after the catalyst. pores, as a function of concentrations at the pore mouths, in
units of kg-mole/see/m* of geometrical surface area. In the
REACTOR MODEL above scheme, the total rate of disappearance of CO is given
In order to obtain kinetic information from the integral bv the sum of (6) \, and f71.
., As stated before. our model
conversion data, a reactor model was devclopul and applied accounts for all known mass and heat transfer effects except
to the laboratory results. In this model the catalyst is divided for pore diffusion. As shown by (7), the resulting apparent
in the axial direction into a large number of cells. Within each activation energy for the C-NO reaction, in the presence of
cell the solid and gaseous temperatures, the concentrations of the competing CO-O, reaction, is - 45.7 kJ.
all active species in the bulk gas, as well as their concen- The solid lines of Fig. 1 illustrate the agreement between
trations at the geometrical surface of the supported catalyst, a few of our observed and calculated NO conversions, using
are the dependent variables. The rate processes occurring (6) and (7). The reader may think that a zero, or even a small
within the cell are then expressed mathematically in terms of positive activation energy in (7) would lead to similar results.
these dependent variables and the catalyst properties. The After all, the larger activation euergy of the CO-Or reaction
rate processes included in the model are the transfer of heat assures that a greater fraction of CO is oxidized by Or, with
and mass by bulk gas flow, interphase heat and mass transfer increasing temperature, leading to concomitant smaller con-
between the gas and the catalyst surface, chemical reaction on versions of NO. This argument is quantitatively incorrect,
the catalyst and the accompanying heat generation, and axial however. To illustrate this, we eliminated the activation term
heat conduction through the monolith. The rate expressions in (7), and readjusted the remaining three parameters to give
are then related to each other by means of steady state mass their best possible fit of the experimental data. The resulting
and energy balances applied to both the gas and catalyst equation,
phases, resulting in a set of coupled nonlinear algebraic equa-
tions which may be solved for the concentrations and tem- dWO1 2.33[CO]~O]895
peratures in each cell. (7)
dt (1 + 1.13 x 108]Or]O.4
The form of the rate expressions are straight forward ex-
cept for the chemical reaction rates (i.e. the catalyst kinetics). when inserted into our model, leads to the dashed lines of
In this model we have chosen to express the kinetics in terms Fig. 1. The agreement is substantially worse than that pro-
of catalyst temperature and ;;surface concentration of each vided bv_ (7).
. ,_with its negative activation enerav.
__ In fact. a
species. Thus the pore diffuston effects are not accounted for statistical test[3] on the complete data base of the hypothesis
explicitly by the model, but rather are folded into the kinetic that the improvement in agreement upon using (7) over (7)
expressions. To determine these kinetics, a functional form of is negligible can he easily rejected at the 0.005 significance
the temperature and concentration dependence of the rate is level.
postulated and the best values of the adjustable parameters in What about the CO-NO reaction in the absence of oxy-
these functions are determined, using a parameter opti- gen? Our relatively small data base for that subsystem can he
mization program, by comparing the model predictions with modeled by the expression
the measured conversions over a range of temperatures,
space velocities, and inlet concentrations. This press may 8.84 [CO] lfJO]
-~=WJOI (8)
then have to be repeated, using a different kinetic expression, dt (1 + O.l94[CO] exp (5.26 x lO/RT))
until a sufficiently good match is found for the experimental
data. In general, our kinetic forms have an Arrhenius tem- with some of the calculated and observed integral con-
perature dependence and a concentration dependence which versions shown in Fig. 2. Note that (8) is quite different from
Shorter Communications 493

our kinetics are much more complex. We feel that three of


the ingredients, the competition for CO, the dominance of
one of the two reactions, and a much higher activation
energy for the dominant reaction, are sufficient to reproduce
an apparent negative activation energy for the non-
dominant reaction, in the regime of pore diffusion control.
The negative activation energy of cqn (7) is actually sur-
nrisingly large. We suspect that it might have something to
do with the strong adsorption term in the denominator of
eon (8). This strone CO inhibition may add to the three
ingreddlentsmentioned above to result inthe large, negative,
apparent activation energy for the C&NO reaction in the
presence of oxygen.
The additional ingredient may be visualized as follows.
The C&NO reaction obviously depends critically on the
Fig. 1. Space velocity: M,OOOhr-. Inlet concentrations: CO concentration which, in turn, is controlled by the
major diluent: N,, with 10% H,O, 12%CO,, 2Oppm SO*, dominant CO-O, reaction. At the lower temperatures, a
plus: A, 1.33% CO, 1000 ppm NO, variable Or, at 37 1Oc; 0, moderate decrease in CO concentration due to pore
1.33% CO, 1000 ppm NO, variable O,, at 482C; 0, I .CU& diffusion limitations can provide an enhancing effect on the
CO, 1000 ppm NO, variable Or, at 593C: p, modeled CO-NO reaction, via the CO-inhibition term in (8). At
with eqn (7); -----, modeled with eqn (7). higher temperatures this term becomes smaller, thus less-
ening the enhancing effect and contributing to the apparent
negative activation energy (eqn 7) of the C&NO reactio-.
in the presence of oxygen. This analysis assumes that eqn
(8), though falsified by pore diffusion effects, qualitatively
rcflccts the intrinsic kinetics of the CGNO reaction, since
it applies to data for which the competing, and compli-
cating, C-r reaction is absent.

Engineering and Research Staff


Ford Moior Comoanv r .
MAX BEITMAN
NORMAN C. O-l-l-0
NOTATION
concentration of A
concentration of indicated species, in
mole fractions
WOI d[NOl
surface. reaction fluxes, in kg-mole/sec/ms
Fig. 2. Space velocity: 930,000 hr- . Inlet concentrations: drdr of geometrical surface area
0.18% CO, 2440 ppm NO, with 10% H,O, 12% CO,, D, effective pore diffusion constant
20 ppm SO,, balance N,. Curve modeled with eqn (8).
E,>Ez activation energies
k,>k, first order rate constants
=n,=c reaction rates
(7). Both are falsified by pore diffusion effects, but (8) R gas constant, J/g-mole/deg. K
predicts conversions which monotonically increase with tem-
RP pellet radius
perature, as indeed is shown by the measured conversions. T temperature, deg. K
tl effectiveness factor
DlSCUSSlON
If the intrinsic kinetics for both CC&NO and CO-O, REFERENCES
reactions were first order in CO and zero order in the other [l] Rajadhyaksha R. A. and Doraiswamy L. K., Catal. Rev.
components, our example would correspond exactly to eqns Sci. EPWZP 1976 13 209 (see D. 236).
(1x4) of the introduction. It would also correspond to [2] E.g., G&tldhi H. S., Piken A.=G., Shelef M. and DeLosh
approximation (5), since we know that the CM, reaction R. G., SAE Trans., Section 2, 85, paper 760201 1976.
predominates in our regime of inlet concentrations. Clearly, 131 Hamilton W. C., Acra Crysr. 1965 18 502.

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