DIFFUSION AND REACTION IN POROUS CATALYSTS

N O R I A K I WAKAO
C;lirersitj o/

AND J .

M . SMITH

Culi/ornin. n a r i s . CulJ

Using a previously developed concept of diffusion in bidisperse porous catalyst pellets, an expression for the effective diffusivity i s derived for diffusion under reaction conditions. This diffusivity i s a function of the effectiveness factor, E,, of the microporous particles composing the catalyst pellet and reduces to the normal diffusivity when Ei becomes unity. The diffusion results are applied to the problem of evaluating the effectiveness factor, E,, of the entire pellet. Charts are given for predicting E, for a first-order, isothermal reaction, in terms of a micropore diffusion parameter, a macropore diffusion parameter, and a reaction rate

, parcmeter. To evaluate E requires a knowledge of the macro- and micropore size distributions, the micro effectiveness factor, E t , and either the average reaction rate per pellet or the reaction rate constant, k,. The method i s based upon a simple model of the pore structure. The model contains some unrealistic simplifications with respect to the actual mass transfer processes in porous materials. Hence the procedure should not be regarded as a general one applicable to all types of porous catalysts.

m m the effectiveness factor \vas introduced by Thiele S 3 there has been copciderable ipterest-for : ) 1 example il. -7. 1 5 ) P i n evaluating the averaqe reaction rate in a porous catalyst. This reqilirrs a n effective diffusivity for the reactant fluid in the porei of the solid material. Accordinqly, attention has been focused recently on measurement and prediction of diff(ision rates (1-6.9. 7 7 . 72. 77). These studies have al\va>-s been considered from the standpoint of diflusion in the abpence of chemical reaction. Experimental nieasuremer ts have been geperally made for diffusion thr0ug.h catalyqt pellets. which in itself is not equivalent. in most instance-. to diffurion under reaction conditions. I n the present Lvork the first objective is the effect of chemical reaction on the difTusion rates. Using the results E O obtained. expressions are then developed for predicting the effectiveness factor for a n isothermal. first-order reaction in a spherical catalyst pellet of known pore size diqtribution. In this \vork the catalVtic material is supposed to be a pellet Lvhich coptains both macro- and micropores. This type of material is ohtainrd Lvhen the catalyst is prepared by pelleting microporous po\vder. T h e effectivenecs factor development i r rirnilar to that of Mingle and Smith (7). in that catalysts Lvith bidicperse pore systems are treated. Hokvever. since the earlier paper a more accurate expression has been derived f,?. (?. 7-71 for diffu5ion in pores where both Knudsen and bulk diffusion are significant. This result has been used by LVakao and Smith ( 7 I ) . along \vith a new concept of pore geometry. to develop a method of predicting diffusion rates as a function of pore 4ze distribution. T h e method gave results in good agreement with ruperimental diffusion d a t a for alumina pellets covering a wide denrity range. T h e baiic conclusion that the diffu.ion rare is proportional to the square of the porosity (Equation 3 ) \vas also drveloped independently by \leisz and Schwartz ( 7 6 ) . This permits one to determine the effect of reaction upon diffusion-the first objective of this paper.

The result can then be used to calculate effectiveness factors without making assumptions regarding. the controlling type of diffusion in the micro- avd macropores. ar \vas necessary in the earlier paper (7). For example. diffuriori in the macropores (the space betlveen powder particle?) may be predominantly by a bulk mechanism in lo\v-den<ity pellets. while in high-density pellets Knudsen diffurion is significant. More importantly. it has been shown ( 7 0 that for low-dmsity pellets mass transfer is primarily through the macroporeu. while in high-density pellets micropore diffusion becomes dominant. Thii sugqepts that mass transfer does not occur. except in lo\v-density pellet<. by the series cteps of diffupion first through the macropores and then into the interior of the powder particles by micropore diffusion. This wries concept was employed in the Mingle and Smith development.
Effective Diffusivity under Reaction Conditions

T h e derivations that follow are based upon the follo\ving assumptions :

1 . T h e reaction is first-order. or pseudo-first-order and reversible. so that the rate of reaction per unit mass of microporous particle is given by

T h e reactant mole fraction. ,Y, applies to the macropore region and j p is the equilibrium value. T h e effectiveness factor. E,. is for the microporous particle. Thus E , f j - ji) can be interpreted as a n average driving force for the particle expressed in terms of the composition a t the particle siirfacr that is. in the macropores. 2 . The catalyst pellet is a t a uniform temperature. 3. Significant reaction occurs onl>-Lvithin the particlPs.
~~~

In catalvst pellets Ivith bidiqperce pore systems the iurracr is almost entirely in the micropores. This is the hapic for assumption 3 .
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Figure 1 is the model proposed by the authors (14) for diffusion in a pellet. It is clear that the arrangement of pores and solid material in the model does not represent the real geometry of a n actual porous material. For example. the asqumption that all the macropores are parallel to the direction of diffuFion is not true. However. the model can be analyzed quantitatively for the problem of combined diffurion and reaction. For these conditions the driving forces for reaction are indicated a t the side of Figure 1. It is supposed that the pellet is a statistical assembly of microporous particles and that volume void fractions are the same as area void fractions. I h e dotted squares (Figure 1) represent the microporous particles. Denoting t,: t i . and td as the several volume fractions,
r l

16:I - % ;
, l

DRIVING FORCE FOR REACTION MACRO PORES

/ Ye _Y _-_ _ _ _

'Y,)

' E , ' I-,

L .:.

*~

Figure 1 .

Model of diffusion and reaction in catalyst pellet

Ea

+ +

(2)

Here Db is the bulk (molecular) diffusion coefficient in the system

T h e statistical arrangement of macropores is such that the effective area void fraction on a contact plane is e a 2 . Similarly. the area fraction of particle-particle contact is (1 The length of the unit cell. in Figure 1: is taken as the distance Ax between the center of one particle and that of the next one. T h e concentration difference over the distance ) u is ( d y l d x ) A x in the macropores and E,(dy d ~ l in the micropores. Diffusion in a unit cell is assumed to be the sum of the following contribution5 :
I

A + R, a = 1

+ (.VR '.YA)

(6)

and D,;, D,, and are the Knudsen diffusivities for reactant species A in the macro- and micropores. respectivel).. They are evaluated from mean macro- and micropore radii, a, and ai: as follows:

Dka =

2 FAa,'3:

D,,= 2 F A n r ' 3

(7)

Substituting Equations 4 and 5 into 3, one obtains

1. Diffusion through the macropores with an area of ea2 and concentration difference (4);'dx) Ax. 2 . Diffusion from a particle to the adjacent particle through the micropores with a n area of (1 - e n ) Z and concentration difference E , ((<>'d.u)k.T h e effective void fraction of micropores per unit area of this section is the square of the void e , ) ] * = [ e , (1 fraction: [ e Z ' (e, 3. Diffusion through macro-micropores in series with an area of 1 - ea2 - (1 - e , ) 2 = 2e,(1 - e a ) , Becauseofthelow diffusion rate in the micropor'es as compared ivith that in the macropores. it is assumed that diffusion through the micropores is the controlling. step in the series p' th.

where

The diffusion from macropores into the microporous particles in the lateral direction is accounted for in the micropore effectiveness factor in Equaiion 1 . Hence. the sum of the three listed contributions gives the total diffusion rate of reactant A per unit cross-sectional area of the pellet. T h e result is:

(Mechanism 1)

(Mechanism 2)

(Mechanism 3)

Equations 8 and 9 are based upon constant total pressure. This is exactlv true in a reaction system only when there is no change in number of moles as a result of reactions. Hobvever. the equations are approximately true for pseudo-firstorder reactions if the change in moles is not large, as pointed out by Scott (70). Equation 9 shows that the effective diffusivity under reaction conditions io a function of the particle (microporous particle) effectiveness factor. E,. A s the reaction rate decreases, E , approaches unity and Equation 9 becomes an expression for the diffusivity in a nonreactive system. This result is identical to that obtained in the diffusion paper (74) when the assumption regarding- contribution ( 3 ) to the diffusion rate is taken into account. If the reaction rate is very fast. E , decreases and the micropore contribution to the diffusion rate decreases. This means that the equilibrium gas concentration prevails everywhere in the mic;oporous particles. Diffusion then is limited to the macropores-that is. only the first term of Equation 9 is retained.
Effectiveness Factor for Catalyst Pellet

A s described by LVakao and Smith

( 7 4 ) . the factor of 4 in the

. i t steadv state. the reaction rate in a differential volume of pellet is equal to the difference in the diffusion rate across t h e volume For example. in a one-dimensional case :

contribution of mechanism 3 arises from a factor of 2 from the area and a second facror of 2 from the diffusion path length of A t '2. The composite diffusivities. D, and D,. macrofor and micropores as developed in the diffusion paper (74) are :
1

Substitution of Equations 1 and 8 into 10 gives

u, =
124

e12

(1 -

(I -

ay) D ,

+ 1 D,,

eay

P d - - dr ( D R T --

2) +

k , . p B E L ( y- v e )

ill)

l&EC FUNDAMENTALS

It'hen Equation 11 is solved Lvith appropriate boundary conditions, the average reaction rate. ?. for the entire catalyst pellet can be expressed in terms of the reactant concentration on the external surface of the prllct. [$-hen the height of the slab is 2L and both end faces are in contact with the reactant concentration ofy,. the boundark- conditions are
x =
h

Differential equations analogous to Equations 13 and 14 can be written for the particles using Equation 19 for the effective diKusivity. T h e solution gives a n expression for E , just as the solution of Equations 13 and 14 gives an expression for E,. T h e results are:

0; dy d.x

0 Equation 20 allows one to evaluate E , from a knowledge of k , and Dtg. Except for very large particles and fast reactions Ei should approach unity (8).
Pellet Effectiveness Factor

L,.y

= yo

Similarly. the equation for a spherical catalyst pellrt is

and boundary conditions are

h

General Solution. Usually, Dklwill be small compared with Db. so that Equation 9 may be simplified as follows :
=

0 ; dy 'du

0
-

Y =

'Yo; y

= yo
Db

: :

I n general. these equations cannot be solved analytically because the diffusivity. Equation 9. is a function of y. T h e general solution by numerical methods is presented later, but it is interesting a t this point to consider the special case of a = 0.
Pellet Effectiveness Factors for a

&,

=0

For numerical solutions it is convenient to write Equations 13 and 14 in terms of new variables 17 and t and parameters, A. a. and B: all of which are dimensionless. I n this form E q u ations 13 and 14 become :

LVhen the ~nolecular\\.eight? of both reactant and product species are the same. a = 0. Then analytical solutions to Equations 11 and 1 3 are possible. T h e resulting expression for the average rate for the entire pellet is:
r' = k&,

E,

bo - y e )

(1 5)
where Equations 24 to 28 define the new variables and the parameters

where the macroeffectiveness factor, E,, is given by: For slab pellet

For spherical pellet

These expressions can be used to determine E, and hence the required average rate. 7. from Equation 15, provided I), k,. and E , are known. T h e effective diffwivitv. D. can be obtained from Equation 9 with a = 0. T h e reaction rate constant, k,, must be determined experimentally. A method of predicting E , is given in the next section.
Effectiveness Factor for Microporous Particles

T h e powder particles are assumed to be spherical and considered to contain only micropores. Hence. the effective difis fusivity for the particles. D,,, given by Equation 5 expressed as

T h e effectiveness factor can be expressed in terms of the average rate. 7, for the pellet as follows:

D,,= -

:t ,

1-aay
Db

+-1

Dkt

is the void fraction of the particle. where Because Dkiis small coinpared with Dh, this can be simplified
to
Dip

Solving this expression for E, and converting the results to the dimensionless parameters gives

= ~tp'Di:i

(1 9)
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or E,
=

~;i3~~;(31) j J ztw

All2

Equations 22. 23, and 31 \yere solved numerically using an

I B M 1620 computer for various valuei of the microdiffusiori parameter, B , macrodiffusion parameter, a , and reaction rate parameter. A. T h e results?shown as plots of the pellet effectiveness factor. E,, are given in Figure 2. For the case of a = 0 (corresponding to a = O ) , Equation 17 gives the solution for E,. In terms of dimensionless parameters Equation l - may be written
m - qrn "

"*
F
=
'(1

coth(

3 (B$-,.
~~~~~

(B-+x

B+1

;>
--)z --I

1
(32)

IC0

This analytical result was compared to the results obtained by extrapolating the numerical solution for finite values of a to n = 0. T h e agreement was good in a11 cases, lending confidence to the numerical rvork. Figure 2 shows the expected decrease in E, with an increase in reaction rate--i.e., reaction rate parameter X. \Vhen the average pore radii increase. D,, and D,i also increase. 'This results in higher values of u and B . Figure 2 shows the magnitude of the increase in E, due to this reduction in diffusional resistances. The method of using Figure 2 ro determine the pellet effectiveness factor may be briefly summarized. First it is assumed that the reaction rate is first-order-that is. Equation 15 is applicable. The effectiveness factor for particle E imust be krio\vn. I t can be determined from rate measurements on the particles as described by Rao. Lt-akao. and Smith (8) for the orthohydrogen conversion. If the poxvder particles are small (less than a few hundred microns). E , is likel>-to be nearly 1 .O. From pore size measurements rhe quantities e,. e l , and a,, and can be obtained, as described by Wakao and Smith ( I 1 ) . 'The value of a w n be ascertained from the stoichiometry of the reaction. Then parameters B and a are established from Equations 26 and 2'. If rhe reaction rate constant. kw. is known, X is determined from Equation 28 and E, read from Figure 2. If instead the reaction rate: i.. for the pellet has been established, a trial and error procedure is necessar>-. A value of k , or X is assumed. and & is obtained from Figure 2. Then the value of the product (k,E,) is checked by comparison with Equation 15. Evaluation of the method Jvith data for the ortho-parahydrogen reaction is considered in the following paper (8).
Acknowledgment

lo0

IO0

The authors express their appreciation to R. De Vogelaere, Department of Mathematics. University of California. Berkeley, for devising a numerical method for the solution of Equation 13. Yu Chang carried out the necessary computer rvork and his assistance is gratefully acknowledged.
ID

loo

Nomenclature
R

.,?-

= = = = = =

macropore diffusion parameter defined by Equation

27

Figure 2.

Pellet effectiveness factor

0, fii

I)
Dh
126

mean radius for diffusion in macropores? cm. mean radius for diffusion in micropores. cm. micropore diffusion parameter defined by Equation 26 effective diffusivit?. in catalyst pellet under reaction conditions. s q . cm. sec. binary bulk diffusivity. sq. cm., sec.

I&EC

FUNDAMENTALS

D,D

effective diffusivity for microporous particle. defined by Equation 18: sq. cm.,sec. fi,, = mean Knudsen diffusivity of gas A in macropores: sq. cm.,sec. Dk, = mean Knudsen diffusivity of gas A in micropores, sq. cm. Isec. E, = effectiveness factor of catalyst pellet E, = effectiveness factor defined for microporous powder particles hI,, h, = Thiele modulus defined by Equations 16 and 17, respectively = reaction rate constant defined per unit time per unit mass of catalI,st, g. mole/g. sec. = half thickness of slab-shaped pellet. cm. = diffusion rate per unit time per unit area of pellet, g. mole,./sq. c m ~ sec. = total pressure, atm. = average reaction rate per unit time per unit mass of catalyst pellet, g. mole/g. sec. = reaction rate (rate of conversion of reactant) per unit time per unit mass of powder particle, g. mole/ g. sec. = gas constant, cc. atm./g. mole O K . = X 2 X/X, = temperature, K . = mean molecular velocity, cm./sec. = distance variable, cm. = mean radius of powder particles, cm. = mean radius of spherical pellet, cm. = reactant gas mole fraction in macropores of pellet = equilibrium mole fraction = reactant gas mole fraction at external surface of pellet
= =

et
elp

= rnicrovoid fraction in peliet

=

e,

X
PB

pp

= = = =

microvoid fraction in particle solid fraction in pellet reaction parameter defined by Equation 28 density of pellet, g Icc. densit! of particle, g.;cc.

literature Cited

(1) Beek, John, A.I.Ch.E. J . 7 , 337 (1961). (2) Carberry. J. J.. Ibid., 7 , 351 (1961). (3) Evans, R. B., LVatson, G. M., Mason, E. . .Gaseous Diffu4. sion in Porous Media at Uniform Pressure, IMP-AEC-15, Inst. for Molecular Phvsics. Lniv. of Marvland, June 1. 1961. (4) Henry, J. P.. Chennakesanan. B.. Smith. J. M.. A.Z.Ch.E. J . 7. 10 (1961) (5) Ho&sch&en, J., znd. Eng. Chem. 47, 906 (1955). (6) Masamune, S.. Smith. J. M., A.I.Ch.E. J . 8, 217 (1962). , , ( 7 ) Mingle, J. O., Smith. J. M., Ibid., 7, 243 (1961). (8) Rao: M. R., Wakao. Noriaki, Smith, J. M., IND.ENC.CHEM. FUKDAYESTALS (1964). 3, 127 (9) Rothfeld, I,. B., LVatson, C . C., Gaseous Countrr Diffusion in Catalyst Pellets. 54th 4nnual Meeting: A.I.Ch.E., hTew York, Dec. 3-7. 1961. (10) Scott, I . Can. J . Chem. Ene., to br published. ) S., (11) Scott, I. S.. Cox. K. E., J . Chim. Phys. 57, 1010 (1960). ) (12) Scott. L). S.. Dullirn, F. A. L.. A.I.Ch.E. J.. to be published. (13) Thiele, E. i V . , Znd. Ene. Chem. 31, 916 (1939). (14) klakao. Noriaki, Smith, J. M., Chem. Erie. Sci. 17, 825 (1962). (15) Whmler, Alborn. Catalysis, Vol. 11, Reinhold, New York,
1955.

(16) Weisz, P. B., Schwartz, A. B., J . Catalyris 1, 399 (1962) (17) Wicke, E., Kallenback, R., Kolloid Z. 97, 135 (1941). RECEIVED review April 5, 1963 for ACCEPTED December 30, 1963 Project carried out with the financial assistance of the U. S. Army Research Office, Grant No. DA-ARO(D)-31-124-G191.

aiy = 1
=

- Je)/!Jo(1VR/lVA)

J,)

macrovoid fraction in pellet

DIFFUSION AND REACTION RATES IN T H E ORTHO-HYDROGEN CONVERSION

M. RAJA RAO, N O R l A K l WAKAO, AND J . M . S M I T H
Cni~ersityof Californza, Davis. Calif.

Rate studies were carried out for the ortho-para-hydrogen conversion using single-pellet catalysts of N i O on A1203. Measurements were also made with the powder particles of catalyst used to prepare the pellets, From these data the effectiveness factor, Ea, was evaluated for pellets of three different densities and, hence, different macropore properties. Pore size distributions, void volumes, and particle sizes were also measured. This information was sufficient to apply the theory in the preceding paper to calculate theoretical effectiveness factors. The agreement between the experimental and predicted results indicated that the theory was satisfactory for the specific, bidisperse catalysts used in this study. The effectiveness factor, Et, for the microporous particles in the pellets was found to b e unity. It appears that E a will be close to 1.0 except for very rapid reactions using pellets prepared from unusually large catalyst particles.

T tions was first analyzed by Thiele (6).

effect of pole diffusion on rates of solid catalytic reacSince then a considerable volume of literature has accumulated-- for example (3. 5. 7, 72, 74. 75). However, no experimental work has been reported for diffusion measurements under reaction conditions Particularly the relation between diffusivity and pore geometrv. with simultaneous reaction, has not been studied I n a preceding paper, a model developed for diffusion in bidisperse pore systems (70) is applied to the reaction case. T h e object of the present study is to compare experimental results with the foregoing theory.
HE

For the experimental proqram, reaction rates were measured for slab-type catalyst pellets under conditions analogous to those used to develop the diffusion theory. In addition. rate data were measured for the catalyst particles used to prepare the pellets. For these studies the ortho-para-hydrogen reaction was employed wing a 25% NiO on A1?03 catalyst. This reaction was chosen for several reasons: The diffusion process is equimolal and cquntercurrent. This simplifies the diffusivitv equations. because (Y = 0. Temperature gradients. even with large pellets. are negligible because of the low heat of reaction.
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