differ in molecular composition, particularly with respect
to olefins, from virgin gas oils. From the linearity of the data
for the virgin gas oils, the following relationships can be de-
rived :
From Figures 2 and 3, thevalues of a. and bo are 25 and -0.42,
respectively, and the corresponding ones for a1 and bl are 20
and -0.46 for the range of data shown. These values were
calculated by least-squares regression of the data for virgin
gas oils. Relationships of K S to aromatic/iiapht.hene ratio did
not correlate as well as the other rate constants. However,
K z does not change drastically wit,h composition (Nace e t al.,
1971), and it typically varies only from 1.5 to 2.5 at 900F.
The relationships between a , K O ,and K 1 vs. the ratio of
aromat,icsjiiaphthenesas represented in Figures 1-3 appear to
be independent of the level of the paraffin concentrations in
the charge stocks. The data in these figures cover reasonably
wide ranges of paraffin conceiit,rations.
Since catalyst decay in catalytic cracking is considered to
be intimately associated wit,h coke formation, it is interesting
to examine the relationship between the catalyst decay con-
stant, a . aiid cat.alyst coke. Figures 4-6 are plots of a, &,
aiid K l vs. catalyst coke and show a increases and K o and K I
decrease with increased catalyst coke.
The relationship of the coke deposited to the decay constant
is to be c.spectmedsince coke is the major contributor to catalyst
decay. The decay constant, a , however, reflects all causes of
decay such as the adsorption of aromatics and nitrogen com-
pounds as well as t.hat coke which remairis after st.ripping.
From Figure 5 and 6, it is clear that thosecharge stocks which
produce more coke also have a decreased cracking and gasoline
format,ion tendency. Iiit,erestingly, the slopes of KO and KI
with coke are approsimately equal indicating the init,ial
selectivity ( K l j K o ) is largely independent of coke make.
,lverage values of t,he nonstrippable catalyst coke in experi-
ments wit8hcatalyst residence times of 5.0 minutes were used
i n these plots (Kace e t al., 1971).
Tests for Transport limitations in Experimental
Catalytic Reactors
David E. Mears
Union Oil Go. of California, Union Research Center, Brea, Calif. 9662i
I n esperiment,al studies of heterogeneously catalyzed
reactions, one of the first objectives should be to determine
whether the investigation is coriceriied with catalytic kinetics
or with interactions between the kinetics and transport
pheiiomena. T h e intrusion of temperature aiid concentration
gradient,s can lead t o severe deviations in a catalysts per-
formance, in many cases completely disguising the true
kinetics of the reaction. To ensure that kinetic data obtained
The Voorhies (1945) relationship between catalyst coke and
catalyst residence time can be written as,
C = atcb
where C = catalyst coke, t, = catalyst residence time, aiid a
and b are constants. The coefficient a is to a significant extent
a measure of the coking tendency of a charge stock. I t is
reasonable to expect some correlations e u t between a and the
catalyst decay constants. Figures 7 and 8 are, respectively,
plots of a vs. a and n vs. a. Both of the catalyst decay con-
stants inciease n i t h incieasing a, which agrees with the trend
shown 011 Figure 4.
Summary and Conclusions
The kinetic rate constants for the catalytic cracking of gas
oils and subsequent gasoline formation can be correlated with
the aromatic/naphthene ratio for a wide range of virgin
charge stocks. The catalyst decay constant also correlates
directly Kith the aromatic/naphthene ratio. Finally, gas oils
whose composition tends to produce more coke also give lower
cracking and gasoline formation rates and higher catalyst
decay rates.
literature Cited
Akhmetshina, M. N., Levinter, ?*I.E., Tanatarou, 11.A., hlocha-
lov, Y. D., Aeftepererab.Aeftekhim. (hloscow), 1969 (8), 10.
Crocoll, J . F., Jaquay, R. D., Petro/Chem Eng., C-24, November
1960.
Fitzgerald, M. E., RIoirano, J. L., Morgan, H., Cirillo, V. A., App.
Spectrosc., 24, 106 (1970).
Nace. D. AI., Voltz. S. E.. Weekman. Jr.. V. W.. Ind. Eno. Chem.
Process Des. Develop., 16, 330 (1971).
Reif, H. E., Kress, R. F., Smith, J. S., Petrol. Refiner, 40 ( 5 ) ,
237 (1961).
Service, W. J., PetrolChem Eng., C-32, November 1960.
Shnaider, G. S.,llukhin, I. I., Chueva, R I . A , , Kogan, Y. S.,
Kham. Tekhnol. Topl. Masel, 1969 (I), 10.
Voorhies, A., Ind Eng. Chem., 37,318 (1945).
Weekman, V. W., Ind. Eng. Chem. Process Des. Dezelop., 7, 90
11968)
Weekman, 1.W., ibid., 8 , 385 (1969).
Weekman, V.W., Nace, D. hl., AIChE J., 16, 397 (1970).
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3lid-Yearhlee&ng,Philadelphia, Pa., May 1968.
for review October 29, 1970
RECEIVED
ACCEPTEDMay 3, 1971
in an experimental reactor reflect only chemical events,
gradients must be virtually eliminated from three domains:
Intraparticle within individual catalyst particle.3
Interphase between the external surface of the particles
and fluid adjacent to them
Interparticle between the local fluid regions or catalyst
particles
The latter doniaiii equally well could be called intrareactor
Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 4, 1971 541
since it applies to gradients within the reactor as a whole.
While the intraparticle domain has been extensively analyzed
for several decades, the latter two domains only recently
have received much attention.
Criteria are n o x available to estimate whether transport
effects in any domain are significantly altering the experi-
mental results. I n deriving such criteria, perturbation analysis
has proved particularly useful for detecting when deviations
of the rate start to become appreciable. The method involves
expanding the reaction rate expression in Taylor series in
concentration, temperature, or both. Criteria involving
various dimensionless Damkohler numbers (Damkohler,
1936) are then obtained which will hold deviations to a n
acceptable tolerance. This paper compares perturbation
criteria with those derived b y other approaches, and evaluates
means of minimizing transport limitations in experimental
reactors.
Intraparticle Transport
Intraparticle transport has been analyzed for a wide
variety of reaction kinetics, particle geometries, and thermal
behavior, as well-reviewed elsewhere (Petersen, 196513; Satter-
field and Sherwood, 1963). Generally the objective has been
t'o calculate an effectiveness factor, 7 , defined as the ratio
of the actual rate to that which would occur if the temperature
and concentration were constant throughout the catalyst
particle. The solutions show that TJ becomes inversely pro-
portional to the characteristic dimension of the particle in
the regime of strong diffusion influence. Cnfortunately,
direct application of such solutions requires knowledge of the
true kinetic behavior and the intrinsic rate constant.
Jf7eisz and Prater (1954) presented a criterion for the
absence of significant diffusion effects with irreversible
reactions which is independent of the rate constant. I t is
assumed that Fick's first law governs diffusion in the porous
media, that the effective diffusivity, D e , remains independent
of the nature of the reaction, and that the intrinsic catalytic
activity is distributed uniformly throughout. T o ensure 7 2
0.95 in an isothermal spherical particle with a first-order
reaction, the criterion requires:
where is the observed reaction rate per unit particle volume,
C, is the reactant concentration a t the external surface of the
particle, and r p is the radius of the particle. The dimensionless
group, called Damkohler's number for diffusive transport,
expresses the ratio of chemical reaction rate to diffusive
flus. The merit of the criterion is that it is stated in terms of
observables, and a parameter, D e , which is independently
measurable. It also applies t o transport of a gas in liquid-filled
pores if the effective diffusivity is correctly evaluated (Satter-
field et al., 1968). Weisz (1957) later showed by means of a
linear approximation of the concentration gradient a t the
surface that the numerical value on the right is conservatively
0.3 for second-order reactions and 6 for zero order. The
corresponding value for first-order reactions is 0.6 by this
approsirnation.
When strong inhibition by the reaction product occurs,
Ailustin and 'CTTalker (1963) and Petersen (1965a) demon-
strated that the Weisz-Prater criterion can fail. Hudgins
(1968), using a perturbation method, derived a design
criterion to ensure TJ > 0.95:
542 Ind. Eng. Chern. Process Des. Develop., Vol. 10, No. 4, 1971
where aisand Rots are, respectively, the rate expression and
its first derivative with respect to reactant concentration
evaluated a t the external surface. A numerical value of 0.75
appearing on the right side of the equation was rounded to 1
in this derivation. This criterion can be extended to negative-
order reactions by taking the absolute value of the derivative.
For simple power-law kinetics (as= kc,"), the perturba-
tion criterion becomes:
(3)
where n is the reaction order. A nearly identical result was
recently obtained by Stewart and Villadsen (1969) as an
illustration of their orthogonal collocation procedure, which
is also applicable to other geometries and kinetics. Equations
2 and 3 fail for zero-order kinetics because the concentration
deviations are beyond the scope of the perturbation approach.
For this case, the value of 6 on the right obtained by Weisz
is recommended.
For reactions involving a change in the number of moles,
the effectiveness factor relationships are shifted as a function
of the transport mechanism. When the mode of transport
is Knudsen diffusion, Otani et al. (1964) showed that a
pressure gradient develops in the catalyst, but the shift
in effectiveness factors is generally negligible. When molecular
diffusion prevails, a decrease i n moles enhances the transport
while an increase hinders it. Weekman and Gorring (1965)
showed that the influence of a volume expansion or contrac-
tion can be expressed in terms of the volume-change modulus:
e = (. - i ) ~ , (4)
in which Y , is the mole fraction of reactant a t the catalyst
surface and v is the stoichiometric coefficient in the reaction
A + vB.Following Kubota e t al. (1969), the criterion for an
isothermal particle can be modified to:
(5)
I n dilute cases ( Y s<< l ) , the volume-change effect becomes
negligible.
Anderson (1963) applied the perturbation approach t o
derive a criterion for the lack of importance of temperature
gradients in catalyst particles. The reaction is assumed to
follow an Arrhenius temperature dependence. For quasi-
isothermal behavior, the observed rate must not differ
from the rate that would prevail a t constant temperature
b y more than an acceptable amount, say 5%. The resulting
criterion, in terms of Damkohler's number involving heat
transport by conduction, is
where \ A H ] is the absolute value of the heat of reaction, X
is the thermal conductivity of the particle, E is the true
activation energy, R is the gas constant, and Tsis the absolute
temperature a t the catalyst surface. Again a numerical
value of 0.75 on the right has been rounded to 1. This criterion
is valid whether diffusional limitations exist in the particle
or not.
Kubota and Yamanaka (1969), extending the work of
Akehata et al. (1961), derived a criterion involving pertur-
bations in both temperature and concentration. The criterion,
expressed here in our nomenclature, ensures 9 > 0.95 pro-
vided that:
 Diagnostic tests for detecting heat and mass-transfer effects in experimental catalytic reactors are reviewed
and updated. New perturbation criteria are presented for intraparticle, interphase, and interparticle trans-
port in both single- and mixed-phase flow in fixed beds. Emphasis i s placed on the proper choice of reactor
parameters to minimize deviations from isothermal plug-flow performance.
(7)
in which 3rd R f t Sare. respectively, the derivatives of the
rate expre-4oii< \vith respect t,o concentration and tempera-
ture, eraliint,ed a t the surface. While applicable to both endo-
thermic :iiid exothermic reactions, the criterion becomes
imagiiiai.y for rare exothermic cases in which t'he second
term iii the brackets becomes larger than the first'.
The criterion can he extended to these cases for which
7 > 1 by squariiig both sides. For power-law kinetics (except
zero order). 7 = I i 0.05 if:
or i n t e r m - of tlic o1)servcd rate and dimensionlef;sparameters:
(9)
jii which:
E around the particle, rather than within (Carberry, 1966).
Y =
RT,
exprrsscs tlic scn-itivity of the reaction rate to temperat~ure
and :
A1 P
represents the maximum temperature difference that can
exist iii the particle relatire to the surface temperature,
( T - T,?)!T,. Typical values are 10-40 for the former,
and -0.1-0.1 for the latter parameter (McGreavy and
C r e s w d l , 1969). The last criterion can 'also readily be
derived by the orthogonal collocat,ion procedure of Stewart
and Villadl;en (1969).
T h e special case for r h i c h 112 - ?PI is close t'o or equal to
zero requires further consideration. When this occurs, the
heat effect compensates for t,he diffusion effect so that the
rate stay-: nearly constant until the concentration within
the catalyst has dropl)ed t o lehs than 80y0 of the surface
value. Such deviations exceed t,he raiige of applicabilit,y
of ihr perturbatioii approach, so this peculiar case is better
of Petersen (1965b).
described by the asyniptotic anal
The latter method give5 a value of 13 for the right side of
Equation 9 when 71 aiid rp both equal 1.O.
It i-: interesting to compare the criterion of Equation 9
n-ith the more widely known one of Weiqz and Hicks (1962)
for exothermic firqt-order reactioiis:
This relationshii) ivas derived by analogy t,o the isothermal
case, with a conservatire simplification of the differential
equation. The criterion safely predicts positive deviations (7
> 1.05) for esotlierrnic reaction.;, but fails to predict nega-
tive deviations for endothermic reactions. Thus t,he criterion
of Equation 9, which also covers diverse kinetics, appears
more generally applicable.
h criterion for isothermal operation of a catalyst particle
is now apparent from inspection of Equation 9:
(13)
Petersen (1965b), by means of an asymptotic solution, derived
a similar criterion with a value of 0.3 on the right for first-
order reactions.
For most cases encountered in practice, Akehata et al.
(1961) note that the term in Equation 7 accounting for the
intraparticle temperature effect amounts t o less than 10%
of the term for diffusion. Consequently the effect of tempera-
ture distribution within a catalyst particle is usually much
less important than the internal diffusion problem. Transport
limitations occurring outside the catalyst particle must
nom be considered.
Interphase Transport
For vapor-phase systems, the greater part of the resistance
to heat transfer is often in the boundary layer or "film"
This happens because the effective thermal conductivity
of the solid is usually much larger than the conductivity
i n the gas phase. I n the case of a highly exothermic reaction,
the particle temperature can become considerably greater
than that of the bulk stream.
A criterion for detecting the onset of a heat transport
limitation in the film has been derived b y the author (Mears,
1971b) with the perturbation approach. The heat transfer
resistance of the film i s assumed to be lumped a t the surface.
If the obqerved rate is t o deviate by less than 5o/c, the cri-
terion requires:
where Ta is the temperature of the bulk fluid, and h is the
heat transfer coefficient given b y correlations (Gliddon and
Cranfield, 1970; Littmaii e t al., 1969). This dimensionless
criterion is valid whet,her transport limitations exist, in the
particle or not. It shows t8hat interphase heat transport
limitations can be expected when reaction heats and rates
are high, aiid flow rates low (small h).
Note the similarity in form to Equation 6, with h replacing
A / r P . Comparison reveals t h a t the interphase heat' t'ransfer
resistance becomes limiting before the intraparticle resistance
as long as:
Bip = hd,/X < 10
i n which the Biot number expresses the ratio of thermal
resistance of the particle to that of the film. Condition 15
is usually met in laboratory reactors because of the low
flow rates.
For isothermal cases with first-order kinetics, Carberry
(1961) showed that the effect of bulk mass transport across
the film can be aswmed negligible relative to surface-reaction
kinetics provided t h a t :
Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 4, 1971 543
 qk/k,a < 0 .I
in which k , is the gas-particle mass transfer coefficient, and
a is the external surface-to-volume ratio of the particle.
This expression is now readily generalized to other reaction
orders by the perturbation approach, allowing a 5oj, deviation
as before. The criterion can be expressed in terms of another
Damkohler number:
cd = &,/CbkC < 0.15/n
where c b is the bulk fluid concentration. Comparison with
Equation 14 for typical cases shows that heat traiisfer
across the film causes excessive deviations long before mass
transfer becomes limiting. The criterion also shows that
zero-order reactions are not affected by iuterphase transport.
One case in which severe interphase mass transport liniita-
tions might be expected is the trickle-flow reactor, i n which a
liquid reactant trickles down the catalyst pellets while a
reacting gas flows either in the same or opposite direction.
This type of reactor is extensively used in the petroleum
i!idustry for reactions such as hydrotreating and hydro-
cracking of heavy oils.
Satterfield et al. (1969) examined the transfer of hydrogen
across the liquid YiIm for a first-order hydrogenation reac-
tion. I n close parallel to the last criterion, they concluded
that mass transfer from the gas phase to the outer surface
of the pellets will not be a significant resistance provided:
Girp/C*kLs < 0 . 1 5
where kLs, the overall liquid side mass transfer coefficient
can be estimated by procedures outlined in their paper,
and C* is the equilibrium concentration of hydrogen in the
bulk liquid.
An important conclusion was tjhat mass transport through
the liquid film cannot b e a significant limitation unless the
catalyst particles themselves are operating a t a very low
effectiveness factor. T h i s results because the effective diffu-
sivity within the catalyst does not usually exceed a value of
about of that in the boundary layer or film adjacent
to the pellet, aiid the film thickness is always substantially
less than the catalyst radius. T h e same conclusion applies,
of course, to the vapor-phase case discussed previously.
It is now obvious that a criterion can be derived for the
combined intraparticle-interphase case by the perturbation
approach. I n effect, one merely replaces Dirichlet boundary
conditions:
T = T,, C = Cs a t r = rp
with mixed boundary conditions:
x distance. I n experimental reactors, our objective is to elim-
Excluding n - Y b P b close to zero, the resulting criterion for
q = 1 f 0.05 becomes:
where y b and are both evaluated a t bulk fluid, rather than
surface conditions. The analogous criterion to Equation 13
for isothermal operation is then:
544 Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 4, 1971
(16) This equation is applicable to both endothermic and exo-
thermic reactions, predicting the occurrence of positive devia-
tions for the latter.
Interparticle Transport
Trausport effects, occurring both radially and axially,
within the reactor as a whole are particularly difficult to
evaluate and control. If neglected, radial temperature
(17) gradients can lead to reaction rates several thousandfold
greater a t the axis than at the wall (Denbigh, 1965). Less
frequently, bypassing or axial dispersion of mass may seriously
distort the reactor perforrrance.
One commoii approach to minimixiiig these effects is to
adopt the differeritial reactor, in which low coiiversioiis are
taken. But high precision of chemical analysis is required,
and interphase gradients are not always eliminated. T h e
recycle reactor provides a means of operating differentially
while maintaining a finite overall conversion. Flow rates
past the catalyst can then be independently varied to elim-
inate interphase and interpart,icle gradients. The well-stirred
heterogeneous catalytic reactor, in which pellets are suspended
in wire cages attached to a rotating shaft, offers another
alternative. The merits and demerits of these reactors have
been ably discussed in recent reviews (Carberry, 1969;
Smith, 1968).
Integral reactors are sonietimes necessary, however, for
bot,h practical and theoretical reasons. For comples reaction
(18) networks, it may prove difficult to prepare synthetic feeds
which match the composition of the actual fluid a t various
stages of conversion. High conversion data are usually prefer-
able in statistical discrimination between rate espressions of
the Larigmuir-Ilinshel~~oodtype (Dariiard and ?\Iitchell,
1968; Alezaki and Happel, 1969). 13arnard and Xitchell
(1968) cont,end that more accurate results can be obt,ained
by measuring integral data over the whole of the conversion
vs. reciprocal flow rate graph than in an analysis using only
a part of the graph. Moreover, integral data are more selective
because a prospective rate equation is required to satisfy
two conditions: effectively, rate vs. contact time and rate
vs. initial concentration. Differeutial data have only to fit
the observed variation of rate with initial concentration.
But to obtain reliable data from integral reactors, the investi-
gator must take extra precautions to ensure that heat and
mass transfer effects do not interfere.
I n the radial direction, this means enhancing both heat
aiid mass transport. Dilution of the catalyst with inert
(19) solids is often useful because it effectively decreases the ratio
of catalyst volume to wall area for heat transfer. Caldwell
and Calderbank (1969) described strategies for optimizing
reactor performance by varying the dilution ratio with asial
inate the usual rise of the centerline temperature to a hot
spot,. Their analysis, based on a one-dimensional model,
shows that a zero temperature gradient can be imposed
along the reactor length by using a dilution ratio which
decreases linearly with conversion. Since this distributes the
reaction rate uniformly down the bed, the dilution ratio
also decreases linearly with reactor length. This approach
also applies fairly well to practical cases of ninny parallel
reactions provided that the kinetics can be lumped (Hutchiii-
son and Luss, 1970). I n a n actual three-diniensioiial reactor,
radial variai,ions will still occur.
An approximate criterion for evaluating the importance
of radial heat transport limitations has been derived by the
author (Mears, 1971b). It applies a t ally cross section in reac-
tors with linearly decreasing dilution, and at the "hot spot"
in undiluted or uniformly diluted beds. At these locations, the
axial temperature gradient equals zero so the sensible heat
term can be eliminated from the differential energy balance.
-4xial conduction can also be neglected for beds with length-
to-particle diameter ratios sufficiently great that plug flow is
approached (generally Lld, > 30). Sumerical solutioiis (Car-
berry aiid White, 1969; Valstar et al., 1969) of the conser-
vation equations suggest that radial mass transport effects are
usually negligible in comparison to heat transport; thus t,he
concentration can be assumed radially constant. These sim-
plifications permitted a n analytic solution (Chambre and
Grossman, 1955) to the radial temperature distribution.
When the heat transfer resistance a t the wall is iiegligible
(i.e., RoirD> loo), analysis (?dears, 1971b) for a 5% deviation
yields the criterion:
where k , is the effect'ive thermal conductivity of the bed, as
given in correlations such as Agneiv and Potter (1970) and
Yagi and Kunii (1959) for vapor-phase systems and Week-
man aiid Meyers (1965) for trickle-flow, and 6b is the average
reaction rate per unit bed volume a t a given bed depth. I n
integral react,ors the latter can usually be evaluated from
the observed rate const,aiit and the coilcentration a t the
cross section of interest.
S o t e t,hat the fuiictioiial form of this criterion is similar
to Equation 6 with the reactor radius replacing the particle
radius mid the thermal conductivit'y of the bed replacing
t h a t of the pirticle. Since R, >> r p and k , approaches the
order of magnitude of X a t low Reynolds numbers, the
interpart,icle t,ransport problem is usually much more severe
than the intrai)article one.
T h e local rate per unit bed volume is related t'o a,the
average rate per uiiit particle volume, by the expression:
in which e is thc bed void fraction, and b is the ratio of diluent
to cat'alyst volume.
Comparison of Equation 23 with the interphase criterion,
Equation 14, shows that the interparticle resistance becomes
limiting first unless:
This condition is achieved only for low values of the radial
aspect ratio (ROIrP)or high dilution ratio. Thus the magni-
tudes of the heat, transport resistances in experimental reactors
are generally in the order: interparticle > interphase > intra-
particle.
m h e n the heat transfer resistance a t the wall is significant,
the interparticle criterion becomes:
i n which the wall Biot number is a measure of the ratio of the
thermal resistance of the bed to t h a t of the wall. T h e data
of Yagi and Kunii (1959) yield wall Biot numbers of 0.8 t o 2
for R e < 100 aiid 0.05 < r,/R, < 0.2, so the denominator
becomes of the order of 2. Thus heat transfer resistance at the
wall aggravates the interparticle transport problem in small
laboratory reactors.
Dilution t o maintain isothermal operation is not without
hazard, because bypassing effects can influence the conversion
at large dilut'ioii ratios. For cases with uniform dilution,
van den Bleek e t al. (1969) developed a stochastic model
quaiit'itatively describing t'his influence and obtained a
criterion to determine the allowable degree of dilution.
Their criterion eiisiires that the bypassing effect will be an
order-of-magnitude less than 6 , the relative experimental
error (percent) iu the coriversion. Rearranged and expressed
in our nomenclature i t becomes:
where L is here the bed length including diluent. The criterion
can be used in calculating the minimum bed length when t,he
dilution ratio is fixed by requirements of bed isothermality.
I n contrast to the radial case, mass transfer iii the asial
direction must be minimized to prevent significant deviations
from plug flow and lower conversions. Peterseii (1965),
applying the asymptotic solution approach to the case of
isothermal, first-order reactions, derived an approximate
criterion for freedom from asial dispersion effects:
01 = dk,D,/o < 1 (28)
where ka is the rate constant per unit catalyst bulk volume,
D, is the asial eddy diffusivity, aiid ij is the superficial fluid
velocity. In agreement mit'h earlier findings (Wehner aiid
Wilhelm, 19561, it shows that the dispersion effect is generally
negligible except for cases involving short beds and high
conversions. B u t the problem can be much more severe in
trickle flow reactors because of the higher eddy diffusivities.
The author (Meare, 1971a), utilizing perturbation solutioiis
for poiTer-law kinetics (13urghardt and Zaleski, 19681,
derived a design criterion which will hold t,he deviation
in the required reactor leiigth to less than 5%. E s p r e s w l i n
t h e same manner as the last criterion, it requires for the
first-order case:
CY < 0.22 (29)
Thus the new crit'erion is about four and a half times more
conservative than the earlier one. This results because
asymptotic criteria actually indicate the transition region
bet'ween the kinetic-controlled xiid transport-iiiflueiiced
regimes (Peterseii, 1968), rather than the point a t which
transport' effects are just starting to become significant.
To minimize axial dispersion effect,s, the practical expedient
available to the experimenter is to lengthen the bed, which
lowers the axial concentration gradient and, hence, the driving
force for dispersion. Consequently the most coiivenient form
of the criterion is one giving the minimum reactor length
for freedom from significant dispersion effect. Expressed as
the rat,io t,o particle diamet,er, the new criterion hecomes:
I, kbr 20 C,
->20- = -111-
d, Pe, Pe, Cf
in which r is the space time aiid C, and C/ are the initial
and effluent concentrations. The axial Peclet number baqed
on particle diameter:
is a measure of the ratio of convective to dispersive transport.
The advantage of the second equality in Equatioii 30 is that
it puts the criterion in terms of the observed conversion and
Ind. Eng. Chem. Process Der. Develop., Vol. 10, No. 4, 1971 545
the independently obtainable Peclet number. Given in
terms of reactor length, the new criterion is 20 times more
conservative than the asymptotic criterion.
For nonfirst-order reactions obeying simple power-law
kinetics, the corresponding criterion is :
L 20 n C,
->-In-
d, Peu Cf
where n is t'he order of the reaction. This general expression
gives Equation 30 for first-order reactions and zero for zero-
order reactions, which are not affected by axial dispersion.
Kote that the axial dispersion problem becomes more severe
wit8h increasing conversion or reaction order, or with de-
creasing Peclet numbers.
Extensive studies have shown that the Peclet number is
geiierally close to 2 for gases a t Reynolds numbers greater
than 2 and to about 0.5 for liquids when Reynolds numbers
are less t'han 10 (Levenspiel and Bischoff, 1963; Miller and
King, 1966). I n trickie-flow, still smaller values are found
in the liquid phase a t low Reynolds numbers (Hochman and
Effron, 1969; van Swaaij et al., 1969). For example, at a
Reynolds number of 4, typical of bench-scale react'or condi-
t'ions, these correlations yield Peclet numbers of the order of
0.1. Coiisequently, the criterion shows that the minimum
reactor length for freedom from backmixing effect,s may be a n
order-of-magnitude greater in trickle-flow than in vapor-
phase operation.
Empirical Tests for Transport Limitation
While the analytical criteria are useful, estimation of
parameters involved can be difficult a t times. For such cases
a well-established empirical criterion is to run the reaction 011
progressively smaller particle sizes, usually produced by
crushing. If the reaction rate per unit particle volume changes
with diameter, strong transport influence is indicated.
Graphical (Weisz and Prater, 1954) and analyt'ical (Gupta
aiid Douglas, 1967) techniques are available for estimating
the effectiveness factors in this case. When the reaction rate
remains iiidependent of the particle size over an appreciable
range, the reaction is considered free from intraparticle
gradients on the macroscopic scale.
An alternate empirical approach, suggested by Koros and
Nowak (1907), is based on the fact that the rat>eof reaction
in the kinetic regime is proportional to the number of sites
per unit volume (S), but proportional to S to the 0.5 power
in the internal diffusion regime. The test involves pelletizing
mixtures of finely divided catalyst with a n inert powder of
comparable diffusional characteristics. If the fraction of
catalyst in the mixed pellet is f , the ratio of rates must also
be equal to f in the kinetic regime. This method avoids
distortions in the flow field which changing pellet' sizes may
cause.
A common empirical test for the possible iiifluence of
ext,ernal heat aiid mass transfer limitations consists of
checking the effect of flow rate on conversion a t consbarit
space velocity. If no such effect is found, it is concluded t'hat
transfer of heat and mass to the particles does not influence
the reaction rate. Chambers and Boudart (1968) warned
that this diagnostic test may fail because of its lack of sensi-
tivit,y a t Reynolds numbers of the order of 10. This observa-
tion \\'as based on a reanal of the interphase heat transfer
data of D e Xcetis and Thodos (1960). More recent data
(Gliddon and Cranfield, 1970; Littman et al., 1969; Petrovic
and Thodos, 1968) iiidicate that both h and k , remain propor-
tional to between the 0.95 and 0.64 powers of G to Reynolds
546 Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 4 , 1971
numbers as low as one. However, the interparticle heat, trans-
fer coefficient (Yagi and Kunii, 1959) becomes quite weakly
dependent on G a t low Reynolds numbers. Thus, as Chambers
and Boudart noted, this diagnostic test requires very precise
conversion data or an extended range of flow rates.
Design Criteria for Fixed-Bed Reactors
I n designing a laboratory reactor, transport limitations
can be minimized through proper choice of the parameters.
Because of the large Arrhenius effect of temperature on the
reaction rate, maintaining isothermal operation is by far the
most critical considerat'ion. The criteria reviewed provide a
means for assessing the best ways to achieire this.
Reducing the reactor radius, a n obvious choice, is partic-
ularly important since the interparticle criterion depends on it
both explicitly and implicitly. The latter dependence occurs
because the interparticle heat transfer coefficient becomes
effectively proportional to the mass velocity, G, a t Re > 100,
and G is inversely proportional to RO2 (at constant mass
flow). The int'erparticle heat transfer criterion then becomes
effectively proportional to the fourth power of R, and the
interphase criterion to the 1.2 power a t higher Reynolds
numbers. Hence decreasing the reactor radius is a vital step
in minimizing both transport' resistances.
The question then arises as to how far the radial aspect
ratio (RO/rP)may be reduced before wall effects become
serious. Because the packing is more open near the wall, a
larger fluid velocity and lower catalyst bulk density occur
there. As a result the conversion is lower near the wall,
causing an apparent lower activity for the bed.
Kondelik and Boyarinov (1969) calculated the effect of
radial void fraction distribution on reactor efficiency as a
function of Ro/rp. Their model divides the reactor into
annular channels based on statist'ical distribution data and
utilizes the Kozeny equation (Carman, 1956) to compute the
volumetric flow rates in individual channels. Radial mass
transfer is accounted for by a lumped radial mass transfer
coefficient D. I n the Roirp range of 5-10, the calculations
show a minimum in the effective bed activity whose depth
increases with conversion. But the minimum is reduced with
improved radial transfer, and the maximum value assumed
for D still appears to underestimate the contribution from
eddy diffusion. Consequently, the gain in isothermality
through reducing the reactor radius appears to more than
compensate for the slight channeling loss to R J R , ratios as
low as 4. However, wall effects may be more serious in trickle-
flow, so larger ratios should be used for this operation.
Finally, in an existing reactor of larger diameter, dilution
of the catalyst bed with inert particles can be utilized to
reduce heat generation per unit volume. Linearly decreasing
dilution ratios are st,rongly recommended for integral reactors.
But in diluting a bed of fixed length, it should be remembered
that the mass velocity is reduced proportionately a t constant
space velocity. The interparticle criterion shows that dilution
will be advantageous in minimizing radial gradients only if
the reactor is operating a t Reynolds numbers sufficiently low
that the effective thermal conductivity is relatively insensitive
to the mass velocity (Le.) Re < 100).
Conclusion
The elimination of transport influeiices in studies of cata-
lytic kinetics is a complex problem, The criteria presented
provide tools for evaluating and minimizing the various
transport resiatances. Like any diagnostic test, each must be
applied with due caution and understanding. If carefully used,
the criteria can help the experimenter to achieve a more
rigorously defined experimental system .
Nomenclature
a = superficial (outside) surface area of catalyst particle
per unit particle volume, cm2/cm3
b dilution ratio, cm3inert solid/cm3 catalyst
Bi, s thermal Biot number for catalyst particle, = hd,/h
Bi, = thermal Biot number a t the reactor wall, = hwdt/ke
C* = equilibrium concentration of hydrogen in liquid,
g-mol/cm3
C h = concentration of reactant in bulk fluid, g-mol/cma
cf = effluent concentration of reactant, g-mol/cm3
CO =-c initial concentration of reactant, g-mol/cm3
C , = concentration of reactant at outer surface of particle,
g-mol/cm3
d, = diameter of catalyst particle, cm
D, = axial eddy diffusivity, cmZ/sec
De = effective diffusivity in a porous catalyst, cmZ/sec
E = intrinsic activation energy for chemical reaction,
g-cal/g-mol
f = fraction of active catalyst in mixed pellet
G = mass velocity, g/sec.cm2 of total or superficial bed
cross section
h = heat transfer coefficient between gas and particle,
g-caljsrc cm*. C
h, = heat t i , > i i i f i f w coefficient at the reactor wall, g-cal/
sec. cni2 (
I
AH = heat of cLheinica1 reaction, g-cal/g-mol
IC = intrinsic rate constant per unit particle volume, sec-1
for first-order reaction
kb = apparent rate c~onstantper unit bulk catalyst volume,
= k ( l - ~ ) qsec-l , ( 1969).
k c = mass transfer coefficient between gas and particle,
cm/sec
= effective thermal conductivity across reactor bed,
g-cal/sec. cm. C
Iz LS = overall mass transfer coefficient through liquid film,
cm/sec
L = reactor bed length, cm
L o = reactor bed length rvith undiluted catalyst, cm
n = integer exponent in power law rate expression
Pea = axial Peclet number, = d,fi/D,
T P = particle radius, cm
R = gas constant, g-cal/g-mol. O K
R e = Reynolds number, = cpd,/p
R O = radius of tubular reactor, cm
R = observed reaction rate per unit particle volume,
g-niol/sec. em3
= reaction rate per unit bed volume, g-mol/sec. cm3
= derivative of reaction rate expression with respect t,o
concentration, see-
= derivative of reaction rate expression with respect to
temperature, g-mol/sec. cm3.K
s = active sites per unit particle volume,
S.V. = space velocity, = o/L,, sec-1
t = time, sec
T = absolute temperature, K
D = superficial velocity, cm/sec
Y , = mole fraction of reactant a t catalyst surface
z = distance in axial direction, cm
GRI:EK LETTERS
cy = dimensionless axial dispersion number, = d h X / o
P = dimensionless maximum temperature rise, = ( - A H )
D,C,/XT,
7 = dimensionless activation energy, = E / R T ,
6 = relative experimental error in conversion
E = bed void fraction
7 = effectiveness factor
e = volume change modulus = (1 - v ) Y 8
X = thermal conductivity of partick, g-cal/sec. cm . C
p = viscosity, g/sec cm
Y = stoichiometric coefficient
p = density,g/cma
7 = space time = inverse space velocity, see
x = Damkohler number for interphase heat transport, =
(- A H ) &r,/hTb
(cr = Damkohler number for interphase mass transport, =
@r,/k,Cb
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RECEIVED
for review November 2, 1970
ACCEPTED MARCH22, 1971
Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 4, 1971 547