430 Ind. Eng. Chem. Fundam.

1902, 21, 438-447

Experimental Criterion for the Absence of Artifacts in the

Measurement of Rates of Heterogeneous Catalytic Reactions

Rostam J. Madon' and Mlchel Boudart'

Department of Chemical Engineering, Stanford University, Stanford, California 94305

An experimental criterion has been developed to assess whether measured catalytic activity is independent of the
influence of transport phenomena. A simple theoretical analysis and experimental verification of the criterion have
been carried out. This test may be used when heterogeneous catalysis is carried out in batch, continuous stirred
tank, and tubular plug-flow reactors, and is best suited to be used with supported metal catalysts. In this case,
the test should be performed with two or more samples with different metal loading but of similar metal dispersion.
Absence of physical artifacts is established by the constancy of turnover numbers. I f the reaction is exothermic,
the test should be repeated at another temperature.

Introduction fusivities of fluids, it is difficult to obtain the effective

It has been stated (Boudart, 1972; Carberry, 1966;
Satterfield, 1970) that catalytic data should be free from
all transport influences to obtain kinetic rate expressions
and to yield the correct activity or selectivity of the cat-
alyst. Though the dangers are known, it should be em-
phasized that scaling down to laboratory studies is fraught
with problems to eliminate concentration and temperature
gradients both within catalyst particles (intraparticle
gradients) and between the external surface of particles
and surrounding fluid (interphase gradients).
In the past, a number of interesting and useful criteria
have been developed to check for the influence of heat and
mass transfer on observed catalytic rates. Most of these
criteria have been explained in a detailed review by Mears
(1971a). Several criteria have been assembled in Table I.
The Weisz-Prater criterion (1954) for intraparticle diffu-
sion, for which only directly observable quantities are re-
quired, has been criticized for lack of generality by Pet-
ersen (1965a). The Petersen criterion (Petersen, 1965a),
however, does not contain only observables and is hence
more difficult to use. The more generalized criterion of
Bischoff (1967), where the integration of the rate expres-
sion is involved, or that of Hudgins (1968)and Stewart and
Villadsen (1969), where the differentiation of the rate
expression is necessary, all suffer from the fact that the
rate expression must be known, be it the power law type
or the Langmuir-Hinshelwood type law, and if it is the
latter then numerical values for all equilibrium constants
must be obtained before the criteria can be used. Hudgins
(1972) derived a criterion for interphase diffusion, but it
suffers from the same problem as stated above. The
criteria to check for interphase and intraparticle temper-
ature gradients are due to Mears (1971b) and Anderson
(1963), respectively.
To use the several criteria, some of the following ex-
perimental properties are necessary: effective diffusivity
in the pores of the catalyst, the heat and mass transfer
coefficients at the fluid-solid interface, and the thermal
conductivity of the catalyst. A t the low particle Reynolds
numbers used in laboratory packed bed reactors, the ac-
curacy of the value of h obtained from known correlations
is subject to question (Madon, 1975). Though numerous
studies have been carried out for bulk diffusion and dif-
Corporate Research-Science Laboratories, Exxon Research
and Engineering Co., Linden, NJ 07036.
0196-4313/82/1021-0438$01.25/0
diffusivity for different catalysts. Satterfield and Saraf
(1965) have shown that diffusional characteristics may
change throughout a pellet due to compression of the
catalyst powder in a pelletizing machine. Intraparticle
criteria include surface concentrations and surface tem-
peratures. These are usually not known and bulk values
can be substituted only if there are no interphase gradients.
Though the heat transfer criteria can be used to check
for temperature gradients in the presence of diffusion, the
latter effect could cause the rate and activation energy to
be low and the criteria to be obeyed. In the absence of
diffusion with the true higher values of the rate and ac-
tivation energy, the criteria could be disobeyed for the
same reaction.
Finally, the particle size is another important parameter.
Often powders with a wide size range are used in laboratory
reaction studies, and Aris (1957) showed that the mean
effectiveness factor is given by
B = CBia[
i
Aris has warned against using average values for particle
size to calculate 7, and in this light the above criteria could
not be used except by using the largest and hence the most
conservative value for the radius.
Besides using the above correlations, experimental tests
are often carried out to check for diffusion. In a flow
system, if the space velocity is kept constant and then if
the conversion remains constant as the flow rate is
changed, the influence of external mass transfer is said to
be negligible. A similar test is used in slurry reactors where
the constancy of the reaction rate is checked as the agi-
tation of the slurry is increased. Chambers and Boudart
(1966) have indicated that at the low particle Reynolds
numbers encountered in the laboratory the heat and mass
transfer coefficients are quite insensitive to changes in flow
rates, and hence the above diagnostic test may fail to in-
dicate that the reaction rates are free from interphase
concentration gradients. Moreover, this test cannot give
any information regarding intraparticle diffusion.
If activity of a catalyst is affected by altering pellet size,
then this activity is said to be influenced by pore diffusion.
However, if there is no change in activity with pellet size
one cannot say for sure that there are negligible intra-
particle concentration gradients. The influence of internal
diffusion in the small pores of a bimodal pore distribution
may still be important, and the test may just indicate that
there is no diffusional influence in the larger set of pores.
@ 1982 American Chemical Society
 Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982 439

Table I. Various Criteria Used t o Check for Transport Effects in Heterogeneous Catalysis
For Intraparticle Mass Transfer For Interphase Mass Transfer
Weisz and Prater (1954) Hudgins (1972)
R2r R, 0.15 1
DaII = -G 1 =- <-r(cb)
Cs De Cbk, Cb 1
dr(C)/dC C=Cb 1
Weisz (1957) For Intraparticle Heat Transfer
Dan < 6 zero-order reaction Anderson (1963)
90.6 first-order reaction
G0.3 second-order reaction [ - A H [ R2r RgTs - 0.75
Daw = < 0.75---
Petersen (1965a) AT, E T
For Interphase Heat Transfer
Thiele modulus < fi Mears (1971b)
where [ - A H 1 Rr RgTb - 0.15
X= < 0.15- --
ri(C1, C2, T) hTb E yb
ri(5) = For Combined Intraparticle Heat and Mass Transfer
ri(Cis, C2s3 e.., TI
Hudgins (1968) Mears (1971a)
0.75 1 1 (-AH) dr(C,T)
Dan 4 -r(Cs) -- -( )T=T, <1
De dT
cs 1 dr(C)/dC I c=cs
Stewart and Villadsen (1969) or for power law kinetics
0.77 1 1
Dan < -r(Cs) DaII < -
cs I dr(C)/dC I c=cs In-70)
For Combined Interphase and Intraparticle Heat
Bischoff (1967)
and Mass Transport"
Mears (1971a)
R lr 1+ 0 . 3 3 ~ 7
<
CbDe I
n - 7bPb I(1f 0.33nw)
a Note. This overall criterion provides that the NET distortion of the observed rate will be within 5% of the rate under
isothermal, isoconcentration conditions. There is no guarantee of freedom from individual transport processes.

Table 11. The Koros-Nowak Criterion

[rate of reaction]/[ concentration of active material] = constant
1. [rate of reaction (mol t 3 - I g-l of catalyst)]/[weight of active material per unit weight of catalyst]
= r/f, (mol s'l g - l of active material)
= constant
2. [rate of reaction (mol s - * g-l of catalyst)]/[surface area of active material per unit weight of catalyst]
= r/fa (mol s-l cm-2 of active material)
= constant
3. [rate of reaction (mol s - ' g-l of catalyst)]/[surface moles of active material per unit weight of catalyst]
= turnover number
= r/f,
= constant

Furthermore, changing pellet sizes could cause distortion
in the flow field wkich could affect contacting.
To circumvent the problems stated above, we wish to
develop an experimental criterion which was first suggested
by Koros and Nowak (1967) to check if reaction rates were
free from mass transfer effects. It will be shown that this
criterion can be used as a test for interphase and intra-
particle mass and heat transfer either when they occur
separately or when the physical events are coupled during
the course of a reaction. I t will be shown that when this
test is obeyed there is neither poisoning nor poor con-
tacting of the catalyst due to bypassing and channelling.
Also, deviations of plug flow behavior in tubular reactors
due to transverse and longitudinal temperature and con-
centration gradients (interparticle gradients), backmixing,
and velocity gradients, will cause the criterion to be dis-
obeyed In all future discussion this test will be referred
to as the Koros-Nowak (KN) criterion.
In the following sections, the test will be explained,
analyzed, and finally demonstrated to show that the cri-
terion can be successfully applied when kinetic measure-
ments are to be obtained.
The Koros-Nowak Criterion
The criterion is based on making rate measurements on
catalyst samples in which the concentration of the cata-
lytically active material has been changed. The reaction
rate, in the kinetic regime, is directly proportional to the
concentration of the active material (see Theoretical
Section). The concentration of catalytically active material
may be defined as (a) the weight fraction of the active
material in the catalyst, (b) the surface area of the active
material per unit weight of the catalyst, or (c) the surface
moles of active material per unit weight of the catalyst.
The Koros-Nowak criterion can then be explained by
noting that in the kinetic regime (a) the ratio of measured
reaction rates must equal the ratio of the weight fractions
of the active material in the different catalyst samples, as
long as the dispersion of the active material does not
change from one sample to the next, or (b) the turnover
number (defined as moles reacted per second per surface
440 Ind. Eng. Chern. Fundarn., Vol. 21, No. 4, 1982
mole of the active material) or the reaction rate referred
to unit surface area of the active material must be invariant
as the concentration of active material is changed. Table
I1 summarizes the K N criterion. Another approach is to
plot the logarithm of the reaction rate in mol s-l g-’ catalyst
vs. the logarithm of the surface concentration of active
material; a slope of 1 denotes that artifacts are not influ-
encing rate measurements. Explanations regarding the
deviation of this slope from unity are given in the Theo-
retical Section.
Koros and Nowak (1967) have explained how one can
change the concentration of active material without
changing the dimensions and pore diffusion properties of
the pellets. Their method consists of mixing catalyst
particles with particles of an inert powder and then making
pellets from this mixture. The initial particles in the
mixture must be much smaller than the final pellets used
in the reaction. The inert powder must have the same
diffusional characteristics as the catalyst powder with
which it is mixed. For both metallic and nonmetallic
catalysts this test can be used conveniently as follows. If
we dilute a given catalyst, by the method described above,
by a certain factor a , then for the K N criterion to be
obeyed the observed rate should change for the diluted
catalyst over the initial undiluted catalyst by the same
factor cy. It should be noted that no measurement of the
number of surface sites is involved.
There are two cases when the K N test, carried out by
diluting a given catalyst as described above, cannot be
used. First, when the catalyst has a bimodal pore distri-
bution, internal diffusion in the micropores may be im-
portant in both the diluted and undiluted catalyst samples,
and if the KN criterion is obeyed it may just indicate that
there is no diffusional influence in the larger set of pores.
Secondly, if the particle size of catalysts used in the re-
action is close to the size of the powder from which the
“diluted” pellets are made, as is sometimes the case for
catalysts used in liquid phase slurry reactors, then the KN
test as described above cannot be used.
In the case of supported metal catalysts, concentrations
of active material may he changed by changing the metal
loading on the inert support but keeping the preparation
and pretreatment procedure identical, and the dispersion
of the metal (defined as the ratio of the number of moles
of surface metal to total metal) close for all the catalyst
samples. Techniques (Whyte, 1973; Benson and Boudart,
1965; Wanke and Dougharty, 1972; Benson et al., 1973) are
now available to measure surface areas of the active metal
in supported catalysts. The selective chemisorption of
hydrogen or carbon monoxide has been used by Sinfelt
(1969) on 11 different supported metal catalysts to obtain
reaction rates per unit area of active material. The ti-
tration of adsorbed oxygen by hydrogen first used to
measure platinum surface areas by Benson and Boudart
(1965) has been recently extended to obtain the surface
areas of rhodium (Wanke and Dougharty, 1972) and pal-
ladium (Benson et al., 1973). When surface concentration
of the active material in different catalyst samples can be
measured, the K N test may be carried out, with caution,
for catalysts with bimodal pore distributions. Hence, if
we have two catalysts, 1 and 2, with surface concentrations
of active material f,, and f,, respectively,where f,, = afmg,
then if the concentration of active material in the micro-
pores of catalyst 1 is different from that in catalyst 2 by
the same factor cy, then the K N criterion cannot be used
to check for the effect of intraparticle mass transfer in
catalysts with bimodal pore distributions.
Let us now see how the KN criterion may be used in the
different kinds of reactors used to carry out chemical re-
actions. In all following discussions f, will be used to
denote the concentration of active material. (The dis-
cussions, of course, will also be valid for f, or fa.)
When investigating heterogeneous catalytic reactions in
a batch reactor, the system is assumed to be in a stationary
state, and either reactant consumption or product for-
mation is observed with respect to residence time. The
KN test may be used in a batch reactor system as follows.
Let us take w1grams of a catalyst in which f m = f,, and
note the conversion at a certain residence time t . In a
second experiment, take w 2grams of a catalyst in which
f m = f m , SO that
~2 = wl(fm,/fm,)
and note the conversion at the same residence time t as
the first experiment. If the conversions at the same res-
idence time in the two experiments are identical, then the
KN criterion is obeyed.
Rates are directly obtained (Boudart, 1968; Denbigh,
1966) in the case of continuous stirred tank reactors
(CSTR) operating at the stationary state, and hence the
KN criterion is easily used. The CSTR condition states
that mixing is complete so that all the properties of the
reaction mixture are the same in all parts of the reactor
and in the exit stream. The concept of the CSTR has been
used, by experimentalists in the laboratory, in the form
of the recycle reactor pioneered by Temkin (1962) and the
continuous stirred tank catalytic reactor used by Tajbl et
al. (1966). The recycle reactor consists of a loop which
includes a reactor containing a small amount of catalyst
and a recirculation pump. At the stationary state, when
the flow rate of chemical components in and out of the loop
is small compared to the recirculation rate, the composition
in the loop and exit line is practically identical, thus
obeying the CSTR condition and allowing the rates to be
obtained directly.
In plug flow reactors, rates cannot be measured directly
unless the reactor is operated in a differential manner.
Rather, the conversion of a reactant is obtained at a known
space velocity which may be defined as the molar flow rate
of the reactant divided by the weight of the catalyst. We
must modify the way to use the KN criterion from the
method described above to a method compatible with the
observables in the tubular flow system. Let us define a
quantity analogous to space velocity and denote it by p ,
the active space velocity
p = tiO/wf, (1)
If two experiments are performed and f , is changed but
p is kept constant in each experiment, then the KN cri-
terion is obeyed if the observed conversion is invariant in
both cases (see Theoretical Section). Another way is to
obtain values of conversion at different flow rates and to
plot conversion vs. l / p using a catalyst sample with f, =
fm1. If this plot coincides with the plot when we repeat the
experiment using a catalyst sample with f , = f,, where f,,
# f m , then the KN criterion is obeyed.
Before concluding this section describing the K N cri-
terion, it must be stressed that the test does not require
a knowledge o f the number o f sites involved in the reac-
tion.
Theoretical Section
A. Intraparticle Mass and Heat Transfer. Three
relations on which much of the following discussion will
be based are
r = kvdC,) (2)
k 0: f m (3)

I
1 n@
1 u
Figure 1. Typical plots of In 7 vs. In $J for isothermal and noni-
sothermal exothermic and endothermic reactions (Weisz and Hicks,
1962).
Equation 2 indicates that the observed rate is dependent
on the effectiveness factor which in turn is a function of
the dimensionless Thiele modulus defined in eq 4.
Equation 3 is characteristic for heterogeneous catalytic
reactions taking place in the kinetic regime. The rate of
a catalytic reaction, defined in moles per unit time, is an
extensive property and is directly proportional to the
amount (Le., weight, surface area, or surface moles) of
active material; e.g., if the amount of active material is
doubled then the rate should be doubled. Before pro-
ceeding, we must clarify the above explanation by stating
that the KN criterion is not the same as the well-known
test in which if the weight of a catalyst is doubled, say in
a slurry reactor, the reaction rate should be doubled if
there is no influence of interphase mass transfer. In the
KN criterion, the concentration of active material in the
catalyst, rather than just the weight of the catalyst, is
changed, and in the kinetic regime the reaction rate is
directly proportional to the concentration of active ma-
terial.
Let us consider the curves A, B, and C in Figure 1. The
slope, of any curve, at any point is
dlnq dlnv
p=-=- (-1 Ip Ia)
dln4 dln$
where
CY = 0 for A and B; a > 0 for C; q = v point in question either to the left or right of point b. If
Using eq 2, 4,and 6
r = kd%!(c,)
s is the slope obtained on plotting In r against In f ; s will
be referred to as the Koros-Nowak number or slope.
When
p-0,s-1
and when
p - - -
-1, s 1/2
The former limit corresponds to 7 1, i.e., no intra-
particle diffusion, whereas the latter limit indicates severe
Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982 441
1n@
Figure 2. A plot of In 7 vs. In $J for a nonisothermal exothermic
reaction (Weisz and Hicks, 1962).
Figure 3. A plot of In 7 vs. In $J for a nonisothermal exothermic
reaction (Weisz and Hicks, 1962).
intraparticle diffusion and low values of q. When diffu-
sional influence exists but is small, the limits for curves
A and B are in between those described above: -1 Ip I
0 and ' I 2Is I1.
For the exothermic reaction a similar situation exists for
part b to c (Figure 2). Between a and b, p is greater than
zero and hence s is greater than 1. The largest (d In q)/(d
In 4) will be at the inflexion point a' where s will also have
its largest value. At point b, p is zero and hence s is unity,
similar to the zero diffusional influence point a. The ef-
fectiveness factor at b is higher than unity, and the rate
is hence higher than the true isothermal rate. An easy way
to resolve this ambiguity is to perform the experimental
criterion at another temperature which would move the
s is unity at two different temperatures, then one can be
assured that one is not concerned with the rather rare
occurrence of being at point b. It is interesting to note that
at point c' where q is unity and there is perfect compen-
sation (the rise in the reaction rate due to the increase in
the temperature within the pellet compensates the de-
crease in the measured rate due to the influence of mass
transfer), the value of s will tend to 1/2, indicating correctly
that the exothermic nonisothermal reaction is being in-
fluenced by intraparticle diffusion. As the Arrhenius
number
Y = E/R,Ts (9)
and the heat generation parameter
P = (-WDeCs/XTs (10)
increase, graphs as shown in Figure 3 may arise (Weisz and
-
Hicks, 1962). Here the values of p are greater than zero
m and hence s -
between points P and Q. A t Q and R, (d In q)/(d In 4)
m. Between Q and R, p 0 and s < 1.
It must be noted that if p is a large negative number s may
become less than 0.5 and also zero or a negative number.
442 Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982

Table 111. Numerical Values for the Case of an q = l/A (13)

Isothermal, Irreversible, First-Order Reaction on a
Spherical Catalyst Pellet where
rl d -p s = 1 i @/2)
0.059 50 0.98 0.51
0.14 20 0.95 0.53
0.27 10 0.90 0.55 and
0.37 7 0.83 0.58
0.48
0.67
5
3
0.75
0.55
0.62
0.73
n
r(CJ = ?(CIS,C28, CSs, ..., (15)
0.81 2 0.35 0.82 The apparent rate constant k may be taken out of the
0.94 1 0.12 0.94 function r ( C ) . Hence
0.98 0.5 0.032 0.98
r(Cs) = kro(Cs)
Between R and S, p > 0 and s > 1. Beyond S the argu- r0(CJ may be a power rate law or a Langmuir-Hinshelwood
ments are similar to the isothermal case. type expression.
For an irreversible, isothermal first-order reaction in a
spherical catalyst pellet the above conclusions may be
obtained analytically from results of others (Satterfield,
1970)

7 = #P = ”[
4
coth 4 - i]
dlnq dlnq
-- - 4-
d In 4 d4
2 - 4 coth 4 - 4’ csch2 4
P’
4 coth 4 - 1
See Table I11 for numerical values. It is interesting to note
that for the firsborder reaction considered, at effectiveness
factors 10.8, the Koros-Nowak number is approximately
equal to q.
Computations are not made so easily for other situations,
e.g., nonisothermal reactions. Equations given by Weisz
and Hicks (1962), Carberry (1961), and others have to be
solved and numerical differentiation carried out to give
(d In d / ( d In 4) = P.
It is essential to note that the above analysis for intra-
particle diffusion holds not only for reactions obeying
simple power rate laws but also the more complex Lang-
muir-Hinshelwood rate expressions including strong
product inhibition. Analysis, detailed by Satterfield (1970),
and Hutchings and Carberry (1966), show that In 7 vs. In
4 plots similar in shape to the ones described above are
obtained. Interphase heat or mass transfer influences can
complicate the problem (i.e., when the Nusselt numbers
are low) by being coupled with the intraparticle case.
Hutchings and Carberry (1966) and Carberry (1961) have
shown that interphase heat transfer influence raises q for
exothermic cases whereas interphase mass transfer tends
to reduce 7. Once again the plots In 7 vs. In 4 are similar
to the ones described above. I n short, for all cases with
intraparticle diffusional influence, with or without t h e
complexity of strong product inhibition, intraparticle heat
transfer, and interphase heat or mass transfer, p will
deviate from zero and s will deviate from one.
It should be noted that the value of s equal to unity also
means that the turnover numbers, obtained for different
values off,, must be identical.
Large Intraparticle Concentration Gradients. Un-
der extreme diffusion conditions only a thin layer of a
catalyst particle is useful, and the local curvature and
hence the shape of the catalyst particle is of minimal im-
portance.
Aris (1965), Bischoff (1965), and Petersen (196513) have
demonstrated that the effectiveness factor is asymptoti-
cally h-l for a general case, where A is the normalized
Thiele modulus
7 oc k-lI2 (16)
From eq 2,3, and 16, it can be easily seen that under Severe
intraparticle diffusion conditions for any rate expression
s =
Before ending the section on intraparticle diffusion, a
short corollary may be easily deduced from the above
algebra.
(12) In eq 7, if the concentration function g(CJ is described
by Cisn,where n is the true reaction order, then
where m is the observed reaction order. From eq 8
n = 1 + (m- l)/s (17)
Knowing s from the KN criterion and the observed con-
centration dependence m, one can obtain the true order
of reaction n, for isothermal operation.
B. Interphase Mass Transfer. When the reaction
rate is strongly dependent on the interphase transport of
reactants to the active material on a catalyst
N = k,a(Cb - C,) (18)
As k, is independent of the concentration of active mate-
rial, changing the latter will not change the rate and the
KN number s will be zero.
For porous catalysts, when there is a large interphase
mass transfer influence the effectiveness factor is usually
low, as only the active material at the mouth of the pores
participates in the reaction.
rate = qkg(Cs) = k,a[Cb - c,] (19)
It can be easily shown for a first-order reaction that
rate = k’Cb
where
Remembering that for a severe internal diffusion problem
7 0: fm-lI2 and using eq 3 and 20, we have two bounds when
the KN criterion is used
1. a k , << qk rate = constant Cb and s = 0
2. ak, >> qk rate = constant fm1/2Cband s = y2
Though easily shown for a first-order reaction, the same
limits apply for more complex rate expressions. Values
 Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982

of s between 0 and ‘I2would then indicate a coupled in- In ,f (rurfoce mol g

-1
catalyst)

fluence of the interphase and intraparticle mass transfer.

C. Interphase Heat Transfer. Mears (1973) has
shown that interphase heat transfer effects become sig-
nificant before the corresponding mass transfer effects
unless /3 is very small in which case, of course, problems
due to heat transfer will not arise. In the following dis-
cussion, it is assumed that there is no diffusional influence
and C, is equal to c b . Though the arguments are for
exothermic reactions, endothermic reactions may be
treated similarly.
At steady state, the heat released by the reaction is equal
to that transferred to the bulk fluid.
(-mr= ha(T, - Tb) (21)
Let us change the concentration of active material on the
catalyst from f,, to f,, where f,, > f,,, keeping all other
conditions the same
( - W r i = ha(T,, - Tb) (22)
( - m r 2 = ha(T,, - Tb) (23) I Coupled Interphore Transfer I
As f,, > f,,, r2 > rl and hence T,, > Tal. T,, > T,, > T b
indicates interphase heat transfer influence. Figure 4. Plots of In f, vs. In r , to indicate diagramatically the
Let us use the KN criterion, N1 = N2,to check for in- Koros-Nowak criterion for interphase heat transfer (exothermic re-
terphase heat transport influence. Using the Arrhenius action) and its coupling with interphase mass transfer.
form for the rate constant and separating f, from the
preexponential term, we get As explained before, when there is only isothermal in-
terphase mass transfer influence s = 0. These individual
fm,A’ exp(-E/R,T,,)g(C,,T,,)
- influences of external heat and mass transfer can be cou-
fm,
pled as indicated diagramatically in Figure 4 in order that
f m , A ’ exp (-E/RgTa,)g(Ca, Ts,) a value between s = 0 and s > 1 would be obtained. In
the rare case when the coupling gives s = 1,experiments
fm, done at a new bulk temperature would shift the value of
s from 1 if transport influences are important. For en-
Divide by exp(-E/RTb) dothermic reactions as f,, > f,, and external temperature
gradients are important, N 2 < N1and s < 1.
Mears (1973) has recently shown the relative importance
of transport effects, and the order was interphase heat
transport > intraparticle mass transport > interphase mass
transport > intraparticle heat transport. It is useful to
keep these generalities in mind when using the KN cri-

-
This equality holds if either (case 1): T,,
Tb or (case 2): T,, Tar.
-
Tb and T,, - terion. Figure 5 indicates usual values of N and s for the
KN criterion.
D. Deviations from Plug Flow Behavior in Tubu-
Case 1 is easily explained, as when the surface tem- lar Reactors (Interparticle Gradients). Plug flow in
peratures tend to the bulk temperature there is a minimal tubular reactors may be defined as a state of flow when
gradient and hence negligible heat transfer influence. the flow rate and all fluid properties over any cross section
Case 2. (a) When Tss > Tal > Tb, N1 # N2, there is
-
interphase heat transfer influence. (b) T,, > Tal Tb, Nl
normal to the fluid flow are identical and the residence
time of all volume elements, entering the reactor, is the
# N2. This occurs when by increasing the rate we may
enter the heat transfer influence regime. (c) T,, -
Tb. This is inconsistent with eq 22 and 23 because when
Tal>
same. Deviations from plug flow are due to the influence
of transverse and longitudinal temperature and concen-
tration gradients (interparticle gradients), velocity gra-

- -
sides cannot remain identical. Therefore, when T?, Tal
we must have T,, Tal Tb. Hence, the KN criterion,
-
their left-hand sides are different as r2 > rl, the right-hand
N1 = N 2 , can be used to establish the nonexistence of
interphase temperature gradients.
It is interesting to rationalize the value of s for inter-
phase heat transfer without diffusion when rate expres-
sions are of the type r = kg(C,). As explained above, when
there is no transport influence and f, is increased from
f,, to f,,, the rate will increase from rl to r2 so that N1 =
N 2 and s = 1. If there is external heat transfer influence
then iff,, > f,,, TS2> Taland r i >> r;; it should be noted
that due to the exponential nature of the temperature
dependence the rate r i increases over r2 more than rl’
increases over rl. Hence N 2 > N1 and s > 1 (see Figure
4).
dients, and backmixing in the tubular reactor. Though
longitudinal concentration gradients are always present
in plug flow reactors, these gradients may influence the
transport of reagents by causing them to reach the reactor
outlet more rapidly than they would by bulk flow alone.
Denbigh (1966) has indicated that transverse tempera-
ture gradients most often affect and invalidate the plug
flow assumption. If Tal and T, represent the axial tem-
peratures when catalysts with the concentration of active
material f, and f,, are used respectively, and iff,, > f,,
and Twis the temperature of the wall, we have
T,, > Tal > Tw
for a nonisothermal exothermic reaction, and
Tap < T,, < Tw
444 Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982
interpiare - rmc lntroparticla 0 Transport E'fect,
...........!:......I
..
: ...... ..
.................
0
0.0:
Figure 5. Interphase and intraparticle transport effects. The chart
indicates the trend of the turnover numbers N1 and N 2 when f,, >
f,,, and shows limits for the values of s when interphase and intra-
particle effects exist separately or are coupled together.
for a nonisothermal endothermic reaction.
As the dependence of the rate on temperature is expo-
nential, conversions in the plug flow reactor, where radial
temperature gradients are significant, will change as f , is
changed but p is kept constant. A similar analysis may
be obtained for the problem of longitudinal temperature
gradients.
The relation used for tubular reactors (Boudart, 1968;
Denbigh, 1966) where the plug flow assumption is valid
may be written as
where r here is expressed in mol sd g-' of catalyst. Mul-
tiplying the above equation on both sides by f ,
If there is any significant deviation from plug flow be-
havior due to the influence of transverse and longitudinal
temperature or concentration gradients, or due to back-
mixing and velocity gradients, the above equation will be
invalid.
Hence, if in two experiments using different values of
f, but keeping p constant the same conversion is obtained,
then the KN criterion is said to hold and deviations from
plug flow behavior will be negligible. In the rare event that
a coupling of various transport phenomena causes the test
to be apparently obeyed, the KN criterion should be
conducted at a second reaction temperature. If the test,
at the second temperature, is not obeyed, then transport
effects are influencing the reaction.
Of course a negative result for the test will also be ob-
tained if besides nonideal flow behavior interphase or in-
traparticle concentration or temperature gradients are
present.
E. Poisoning and Poor Contacting of the Catalyst.
Poor contacting of the catalyst may be due to the fluid
channelling and bypassing the catalyst. This case and the
case of catalyst poisoning would result in a certain number
6 moles of active material not being used for the reaction.
It will be shown that when this occurs the measured
turnover numbers, using catalyst samples with different
values off,, will not be the same and the KN criterion will
therefore be disobeyed. In two separate experiments let
the measured rates in mol d 8 - l of catalyst be r< and r2/
and the concentration of active material in surface mol g-l
I
of catalyst be f , and f,,, and the weights of the catalysts
taken be w1 and w2,respectively.
Hence, the calculated turnover numbers will be
In the case when the reaction is carried out under no
poisoning conditions and good catalyst contacting
The "true" rate rl is then related to rl' by
61
r,' = rl - N-
W1
Dividing (28) by f,, and using (26) and (27)
N(fml- 6 1 / ~ 1 )
N,' =
fm1
Similarly
Nfm, -WW2)
N,' =
fmz
N,' and N,' are then equal only when
This is not possible except in the case
61 = Cyf,,W1 (29)
and
6, = afm2W2 (30)
To check for this case the weights of the catalysts should
be changed by an unequal amount (say, w1/2 and w2/3)
and the measurement of the rates repeated. If again
turnover numbers are found to be equal, then there is no
catalyst poisoning or poor catalyst contacting.
Experimental Results and Discussion
The liquid phase hydrogenation of cyclohexene was
studied over supported Pt/Si02 catalysts. The details of
the apparatus, materials, procedure, and results are given
elsewhere (Madon et al., 1978). The reaction was tested
via the above criterion for any transport effects.

in fm (rvrface mol Pt g-1 catalyst)
-I 1 IO
I
0 1 .50% Pt/SiO2 BlOO%
0 2.30% Pt/SiO2 W 62%
0 0.38% Pt/SiO2 BlOO%
V 0.53% Pt/Si02 E= 56%
Figure 6. The Koros-Nowak criterion applied in the study of the
liquid phase hydrogenation of cyclohexene on Pt/Si02 catalysts.
catalyst particle size > 200
Conditions: r corrected for 101.3 kPa H2,
mesh, solvent-cyclohexane = 20 cm3,at 275 K cyclohexene added
= 2 cm3,at 307 K cyclohexene added = 0.5 cm3.
The reaction was carried out with three different size
fractions of Pt/SiO, catalysts: (a) greater than 200 mesh,
(b) 100 to 200 mesh, and (c) 60 to 100 mesh. Observed
reaction rates on the three separate catalyst size fractions
have been plotted in Figures 6 and 7, which are diagram-
matic representations of the KN criterion written as r a
f," and indicate clearly whether mass transport effects play
a dominant role. From Figure 6, we ascertain that with
the catalyst size fraction (a) there is negligible transport
influence as s is equal to 1, whereas with the two larger
size fractions (Figure 7) the observed reaction rates are
found to be severely affected by intraparticle concentration
gradients, the value of s being 1/2. Calculations to sub-
stantiate these observations are given elsewhere (Madon,
1975).
It is also interesting to note the values of the turnover
numbers when catalysts with size fraction (a) were used.
The 1.5% and 0.38% Pt/SiOz samples had the identical
dispersion of 100% and N was found to be 2.67 s-' and 2.51
s-' at 275 K and 9.16 s-l and 9.02 s-' at 307 K. The 2.3%
and 0.53% Pt/SiO, samples had dispersions of 62% and
56%, respectively, and N was found to be 2.40 s-' and 2.33
s-l at 275 K and 8.67 s-' and 8.51 s-l at 307 K. It should
be noted that only catalysts with dispersions that are
identical or very close must be compared when the KN
criterion is used. The identity of the turnover numbers
at two different temperatures is another way of looking
at the test and indicates, as does Figure 6, that the reaction
rates are not influenced by any physical events.
The activation energy of the reaction, using the small
size particles, i.e., when s = 1,was found to be 24.4 kJ mol-l
whereas using the larger size (100 to 200 mesh) particles
when s = 1/2, a value of 18.9 kJ mol-' was obtained.
The rate expression for the liquid phase hydrogenation
of cyclohexene may be written in the form r = kvg(C,). For
Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982 445
In i, (ruriace mol pt g-l catalyst)
-1 I -1 0 -9
I I
0 1 .50% Pt/SiOp D=lOO%
02.30% Pt/SiO2 E= 62%
v 0 . 5 3 % Pt/BO2 W 56%
Figure 7. The Koros-Nowak criterion applied in the study of the
liquid phase hydrogenation of cyclohexene on Pt/SiOz catalysts.
Conditions: r corrected for 101.3 kPa Hz,
solvent-cyclohexane =
20 cm3,cyclohexene added = 0.5 cm3,
severe internal diffusion, 7 = 1/4, and using eq 4, r cc
(kDe)'/2.One may express k and De by simple Arrhenius
relationships (Satterfield, 1970; Satterfield et al., 1968)
De = A, exP(-ED,/R,T)
k = A exp(-E/R,T)
Hence the observed activation energy for the severely in-
ternal diffusion influenced reaction is given by '/z(EDe +
E). Using an activation energy of 12.6 kJ mol-' for the
diffusion of H2in cyclohexane (Satterfield, 1970; Satter-
field et al., 1968), the activation energy of the reaction in
the 100 to 200 mesh Pt/SiO, particles is '/&4.4 12.6)+
= 18.5 kJ mol-'. Though this is close to the observed value
of 18.9 kJ mol-', it must be stressed, however, that using
values of activation energy alone to explain diffusional
influence could lead to errors.
Mears and Boudart (1966) studied the liquid phase
dehydrogenation of isopropyl alcohol on nickel catalysts
reduced with sodium borohydride and on Raney nickel in
a slurry reactor. The slurry was agitated either by stirring
it with a propeller or, to study the effect of mass transfer
under different hydrodynamic conditions, by shaking it.
As the slurry agitation rate was increased the reaction rate
increased and then leveled off to a plateau. It is usually
inferred (Satterfield, 1970) that there is no influence of
external mass transfer on the reaction rates at the plateau
value. Mears and Boudart argued that, at the plateau
value, though the possibility of external mass transfer
influence was eliminated, the rates could still be affected
by pore diffusion. To check the latter point, they prepared
nickel catalysts of different surface areas and noted that
chromium acted as a structural promoter and increased
the specific surface area of the active nickel component.
Surface areas of the nickel catalysts were determined by
the fatty acid adsorption method of Smith and Fuzek
(1946) and by the nitrogen BET technique. At high agi-
tation intensities, the rate constant per unit surface area
remained essentially constant over a sevenfold variation
in the specific area of the catalyst. Mears and Boudart
concluded that this observation provided strong evidence
446 Ind. Eng. Chem. Fundam., Vol. 21, No. 4, 1982
against any influence of internal or external diffusion.
They argued that at low agitation intensities the reaction
rate was reduced as a result of internal (and to a certain
extent external) mass transfer due to catalyst agglomera-
tion and clumping, and with increased agitation the re-
action rate increased due to better suspension of the
catalyst in the slurry with breakup of catalyst aggregates.
The test, performed with several catalysts in which the
surface area of the active component was varied and used
to conclude that reaction rates at the plateau value were
free from both internal and external mass transfer, was
in effect the diagnostic criterion later proposed by Koros
and Nowak (1967).
The Koros-Nowak criterion has also been used suc-
cessfully on vapor phase reactions: hydrogenation of
ethylene (Schlatter and Boudart, 1972),cyclohexene (Segal
et al., 1978), cyclopropane (Boudart et al., 1966), and ox-
ygen (Hanson and Boudart, 1978), decomposition of NO
(Amirnazmi et al., 1973) on supported Pt catalysts, and
ammonia synthesis on supported Fe catalysts (Dumesic
et al., 1975).
Conclusion
An experimental criterion to check for true reaction rates
in heterogeneous catalysis has been developed. If the KN
test is obeyed, at two different temperatures, one can be
sure that the observed kinetic data are free of artifacts such
as mass or heat transport, catalyst poisoning, and con-
tacting. If the test is not obeyed, it may be difficult to say
exactly which physical event is affecting the rate data,
though good characterization of the catalyst used and some
understanding of the reaction being studied may help one
to understand which artifact influences the reaction rate.
The KN criterion cannot be used for catalysts with a
bimodal pore distribution if one uses the dilution method
suggested by Koros and Nowak (1967).
The test may be used with batch, continuous stirred, or
plug flow reactors, and during differential or integral rate
measurements. A simple analysis of the criterion has been
given, and its use in the laboratory demonstrated. Though
in general the test may be used for any catalyst if an ap-
propriate inert diluent can be obtained, it is most readily
and easily used for supported metal catalysts where the
support is inert and for heterogenized homogeneous or-
ganometallic catalysts.
Nomenclature
a = external surface area of catalyst per unit volume of the
catalyst, cm-l
A' = preexponential factor of the rate constant
A = A'fm, A'fa, or A'fw
A, = preexponential factor in the Arrhenius relationship for
D.
c ==concentration,mol cm-3
DaII = Damkohler number of the second kind
DaIv = Damkohler number of the fourth kind
De = effective diffusivity, cm2 s-l
E = activation energy, kJ mol-'
f, = concentration of active material, surface moles of active
material g-' of catalyst
f, = concentration of active material, cm2of active material
g-' of catalyst
f, = concentration of active material, g of active material g-'
of catalyst
g(CJ = g(Cls,C2s,CBs...) = concentration function in the rate
expression
h = heat transfer coefficient, J cm-2 s-l K-l
A H = heat of reaction, J mol-'
k , = mass transfer coefficient, cm s-l
k = rate constant
k' = defined by eq 20
m = observed reaction order
n = true reaction order
AO = molar flow rate, mol s-'
N = turnover number, s-'
N = molar flux, mol s-l cm-3
p = defined by eq 5
r = reaction rate, mol s-l 8-l (or ~ m - of~ catalyst
)
r ( C ) = rate expression, defined by eq 15
R = radius, cm
R, = gas constant
s = Koros-Nowak criterion number or slope
S, = external surface of the catalyst particle, cm2
t = time, s
T = temperature, K
V , = volume of the catalyst particle, cm3
w = weight of the catalyst, g
x = conversion
Greek Letters
a = any integer or fraction
a' = volume fraction
p = heat generation function, defined by eq 10
y = Arrhenius number, defined by eq 9
6 = unused moles of active material, see eq 28 rate
7 = effectiveness factor, defiied as the ratio of the actual rate
for a catalyst particle to the rate evaluated at external
surface conditions
X = thermal conductivity of the catalyst, J cm-' s-l K-'
h = normalized Thiele modulus, defined by eq 14
v = stoichiometric coefficient
t = Ci/Ci,
p = active space velocity, defined by eq 1
I$= Thiele modulus, defined by eq 4
x = defined in Table I
w = defined in Table I
Subscripts
a = property at the axis of a tubular reactor
b = bulk property
i = species 1, 2, 3, ...
s = surface property
eq = equilibrium
Literature Cited
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Denbigh, K. 0. "Chemical Reactor Theory"; Cambridge University Press:
Cambridge, 1966.
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Petersen, E. E. Chem. Eng. Scl. 19658, 20, 587.
Petersen, E. E. "Chemlcal Reaction Analysis"; Prentlce-Hall: Englewood
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SatterfleM, C. N.; Saraf, S. K. Ind. Eng. Chem., Fundam. 1985, 4 , 451.
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Receiued for reuiew September 28, 1981
Accepted May 7, 1982

Mechanism of Stickiness in Hygroscopic, Amorphous Powders

Galen E. Downton,' Jos6 L. Flores-Luna,2 and C. Judson King'

Department of Chemical Engineering, University of Callfornia, Berkeiey, California 94720

Sticking, caking, and agglomeration tendencies of hygroscopic, amorphous powders are interpreted in terms of
a mechanism of viscous flow driven by surface energy during particle contact. The mechanism predicts that
stickiness should occur for combinations of temperature and moisture content corresponding to viscosities of the
amorphous material below some relatively constant value, which for short-time contact should be within the range
loe to 10' Pas. The viscosity is affected by both moisture content and temperature, thereby explaining the inverse
relationship between sticky-point temperature and moisture content for such powders. Both bulk-solution and
powdered specimens of a 7:l w/w mixture of sucrose and fructose were prepared, with moisture contents in the
range of 2 to 7% w/w. Viscosity measurements of the bulk-solution specimens were made with both a falirg-baii
method and a rheogoniometer. Viscosities corresponding to experimentally measured sticky-point temperatures
fell consistently within the range 0.3 X lo7 to 4.0 X lo7 Paos, thereby lending support to the proposed mechanism
and quantitative model.

Introduction operating problems, and powder-handlingdifficulties. For

Dehydration of liquid materials is widely used to pro-
duce stable, easily handled and stored products in an
economical fashion. Several techniques, such as spray
drying, freeze drying, and drum drying, are available for
producing dried powders from a wide range of raw mate-
rials including liquid foods, plastics, detergents, fertilizers,
and pharmaceuticals. One phenomenon frequently en-
countered during production and storage of these dried
powders is stickiness.
A familiar example of stickiness is caking during storage.
Hygroscopic dried foods such as instant coffee or drink
mixes tend to form hard cakes when subjected to high
temperatures and/or humidities. The powder is no longer
free-flowing and, because the cakes are less porous, they
reconstitute less readily. Another example of stickiness,
which can be turned into an attribute, is agglomeration,
a process commonly used with dehydrated powders to
obtain larger, porous particles with better rehydration and
handling characteristics and/or more pleasing and con-
sistent color, shape, and appearance. This operation is
redly one of controlled stickiness; particles are deliberately
subjected to steam, moist air, or a fine mist of water, as
well as repeated contact, so that surfaces become sticky
and clusters form via particle collisions and adherence. In
spray drying, stickiness can be a major problem, which
occurs when particles which are insufficiently dry collide
with one another or with the walls of the drying apparatus
and become stuck. This can lead to lower product yields,
Procter and Gamble Company, Coffee Division, The Winton
Hill Technical Center, 6210 Center Hill Road, Cincinnati, OH
45224.
'Mezquital de Oro, Apdo. Postal 138, Hermosillo, Sonora,
Mexico.
0196-4313/82/1021-0447$01.25/0
heat-sensitive products this can also lead to overheating,
resulting in unpleasant sensory characteristics and/or
degradation. These problems are preventing some
materials-notably fruit juices which contain large
amounts of hygroscopic, amorphous sugars-from being
successfully dehydrated.
Coping with stickiness in spray dryers and in powdered
products and achievement of successful agglomeration have
largely been matters of trial-and-error experimentation to
find conditions which avoid or control the sticky charac-
teristics of a given material. Cooling the dryer walls and
flushing them with cool air have been employed to avoid
stickiness in spray dryers (Lazar et al., 1956; Gupta,
1978a,b). Various additives, often of high molecular
weight, have also been used to combat stickiness in spray
drying (Brennan et al., 1971; Gupta, 1978a,b) and in
powders (Peleg and Mannheim, 1969,1973,1977).
There is as yet no quantitative model which describes
the mechanism of stickiness in dried powders and explains
the success of failure of past approaches to the problem.
Previous mechanistic speculations are nearly all qualitative
and incomplete. White and Cakebread (1966) recognized
dried liquid foods as amorphous glasses, i.e., metastable,
supercooled liquids below their glass-transition tempera-
ture, Tg.At temperatures below Tg, the viscosity is ex-
tremely high, of the order of 10l2Pa.s (Jones, 1956). A t
higher temperatures and/or humidities, the glass assumes
more of a liquid nature, with a lower viscosity. Stickiness
defects, such as lumpiness and caking, were attributed to
this incipient liquid state.
Peleg and Mannheim (1977) attributed caking of onion
powder to moisture absorption and proposed a humidi-
ty-based caking mechanism. In their model, water absorbs
on particle surfaces, forming a saturated solution and
thereby making the particles sticky and capable of forming
0 1982 American Chemical Society