Chmicni Engineering Science, Vol. 44, No. 6, pp. 1275-1280, 1989. OOC9 25W’/g9 $3.00+0.

00
Printed in Great Britain. 0 1989 Pergamon Press pk

ON TEIE SEPARABILITY OF CATALYST ACTIVITY AND

KINETIC BEHAVIOR

DAVID T. LYNCH+ and GERHARD EMIG

Institut fiir Technische Chemie I der UniversitSt Erlangen-Nhmberg, EgerlandstraDe 3, 8520 Erlangen,
F.R.G.

(First received 21 December 1987; accepted for publication in revised $m-m 1 September 1988)

Abstract-The separability ofcatalyst activity and kinetic behavior is examined for several reaction systems
described by elementary-step mechanisms. It is shown that separability is directly related to the form of the
elementary steps in a mechanism. Three general types of mechanisms are described. Activity and kinetics are
always separable for type 1 mechanisms. The converse is true for type 2 mechanisms provided that the
reactant surface coverage is neither extremely high nor low. For type 3 mechanisms, the most commomy
encountered type, separability of kinetics and activity results when one of the steps in the mechanism is rate-
controlling (surface reaction, adsorption etc.), and, conversely, nonseparable behavior is the direct result of
the lack of a single rate-controlling step. It is shown that previous reports of nonseparable behavior can be
adequately described by using type 3 mechanisms. The use of nonseparable activity and kinetics for model
discrimination based on structural differences between mechanisms is also discussed.

INTRODUCTION adjustment of rate data normally involves the quanti-

Catalyst deactivation is an important phenomenon in tative specification of the catalyst activity. Following
the industrial usage of catalysts as well as in the Szipe and Levenspiel (1971), it has been assumed in
fundamental examination of reaction kinetics. For a most recent studies [e.g. Agnew and Shankar (1986),
catalytic reaction to be industrially viable it is usually Mukkavilli et al. (1986) and Pal et af. (L986)] that the
necessary to minimize any deactivation which occurs. activity, (I can be separated from the intrinsic rate
This can typically be done through appropriate cata- behavior, ri, by expressing the overall rate, r, in the
lyst development. or through careful control of the form
feed and reactor operating conditions. If significant
r = a(past history). r,(present conditions) (1)
deactivation cannot be avoided, then catalyst regener-
ation procedures are necessary. Regeneration is often rather than in the general nonseparable form
employed when deactivation occurs by coking or
r= r(past history, present conditions). (2)
sintering, where the operating time between regener-
ations can range from several months, for hydrocar- If thekinetics and activity are separable, then it is
bon reforming on supported noble metal catalysts, to possible to study deactivation independently of reac-
on the order of a minute (continuous regeneration) for tion kinetics. However, it has been shown experi-
the cracking of hydrocarbons using synthetic zeolites mentally that the assumption of separability is not
(Denny and Twigg, 1980). The various aspects of always valid (Bakshi and Gavalas, 1975; &al and
catalyst deactivation have recently been extensively Butt, 1981; Ltie and Tanger, 1987). Nonseparability
reviewed (Hughes, 1984; Butt, 1984). can be accounted for by assuming the existence of a
One of the steps in the systematic development of a nonideal surface (Butt et al., 1978), or by describing the
catalyst is the determination of the reaction rate deactivation via a mechanism composed of el-
behavior as a function of expected operating con- ementary reaction steps coupled in some fashion to
ditions. This information is essential for proper scale- the mechanism of the main (desired) reaction (Corella
up in order to produce the eventual design of an and Asha, 1982). Nevertheless, the separability as-
industrial reactor. In addition, the rate behavior can sumption has routinely been invoked, perhaps be-
be used to infer the detaiis of the sequence of el- cause of the generally held belief that it is valid for
ementary steps through which the overall reaction ideal (in the Langmuir sense) surfaces (Hughes, 1984;
proceeds_ Information concerning the elementary-step Butt, 1984).
mechanism can subsequently be used to produce However, as shown in the following, the existence of
improved catalysts. The occurrence of catalyst deac- an energetically uniform (ideal) surface is not a suf-
tivation adds another level of complexity to the deter- ficient condition for activity and kinetics to be separ-
mination of intrinsic kinetic behavior in that it be- able. As a first step to illustrating this, it is necessary to
comes necessary to somehow adjust the rate data to define a quantity which can be used to quantitatively
compensate for any effects due to deactivation. This describe the interaction between the activity and
kinetics for a system. Such a quantity, p, has been
previously defined by Bakshi and Gavalas (1975):
‘To whom correspondence should be addressed. Per-
J-(c, T; poisoning level i)
manent address: Department of Chemical Engineering, IJni-
ptc. T)= (3)
versity of Alberta, Edmonton, Alberta, Canada T6G 2G6. r(c, T; poisoning level j)’

1275
1276 DAVID T. LYNCH and GERHARD EMIG

If the activity is only affected by the quantity of poison

(fractional surface coverage), then from the combi-
nation of eqs (1) and (3) it is seen that when a system is
separable p will be a constant for any two levels of
poisoning [the ri terms in eq. (1) cancel]. If p is not
where
constant, but is instead a function of concentration
and temperature, then the activity and kinetics are
nonseparable. For separable kinetics it is seen that p is (7)
just the ratio of the activities (usually denoted by a or
s) at two different levels of poisoning. If poisoning level and
j in eq. (3) refers to the fresh catalyst, then p is in fact
identical to the generalized form of the activity as a=~K~CBI(K~I+K~IK~CB~-K~~K,CAI)
(I+K,CAI+K,CB])*
__ (8)
defined by Szepe and Levenspiel (1971), where time
and poisoning level are considered to be analogous.
This measure of separability is primarily intended with the restriction that @>4a due to the numerator
for systems where the catalyst can be dehberately and denominator of eq. (6) both changing sign when /?
deactivated by the addition of measured quantities of is reduced below 4a. For constant values of the rate
an irreversibly adsorbed poison, with rate measure- constants (constant temperature) a and /3only depend
ments performed subsequent to each addition of on the reactant concentrations.
poison. The measurement of p would typically consist It is.readily determined from eq. (6) that p asymp-
of determining the reaction rate for a fresh catalyst at totically approaches either a value of (1 -8,)2 for
several reactor concentration levels at a single tem- small values of c( and /3,or a value of (1 - 0,) for large
perature. These measurements would then be repeated values of these two parameters. Physically, these two
using -a partially deactivated catalyst employing ex- situations correspond to either the surface reaction
actly the same concentration levels and temperature being rate-controlling, or to adsorption of one (or
as for the fresh catalyst. Alternatively, a single concen- both) of the reactants being the limiting step, respect-
tration level could be chosen, and rate measurements ively. Thus, when theie is a single rate-controlling step,
made at several temperatures. For the rate measure- upparenrly separable activity and kinetics can occur
ments it is important that the reactor be operated over a range of operating parameters with p approxi-
iSothermally and in the absence of all concentration mately constant at a value of either (1 --tJ,,)’ or
gradients. While a differential reactor could be used, a (1 - Hp). However, in the absence of a single rate-
well-mixed gradientless reactor is normally a better controlling step, p will vary within these two limits
choice. F&ther details concerning experimental because it will be a function of the reactant concen-
equipment and strategies for the measurement of p trations and the reactor temperature. It is thus seen
have been given by Liiwe (1981). that the widely held belief that activity and kinetics are
separable for energetically uniform (ideal) surfaces is,
for this mechanism, only valid as a limiting situation.
From an examination of several additional mechan-
DETERMINATION OF 0 FROM MECHANISMS
isms it is possible to empirically generalize the pre-
The determination of the form of p for a particular ceding result through the definition of three types of
mechanism composed of elementary reaction steps mechanisms.
can be readily determined from component balances
for the various surface species. For example, for the
(1) A mechanism is type 1 if in each steady-state
bimolecular mechanism (mechanism 1) surface species balance equation, the sums of
A + %$A-S (Ml-I) the powers for the surface species concen-
trations (including the empty site concen-
B + S=B-S (M l-2) tration) are identical for each term in a particu-
A-S + B-S -+C + 25 (Ml-3) lar balance equation. This does not imply that
the sums must be identical between equations.
the steady-state surface species balances, for a con- Activity and kinetics are separable for type 1
stant fractional coverage of poison Q,, are given by mechanisms independent of parameter values.
Many Eley-Rideal mechanisms are of this type.
K,[A](1--8,--8,--8,)--8,--KjIeAeg=0 (4) A mechanism is type 2 if any surface species
(2)
K2[B](1 -Qep-eA-8S)-8s-K 32 8‘
8 B =o
A (5) occupies more than one active site. Kinetics and
activity are inherently nonseparable for a type 2
where K,=kJk_,, K,=k,/k_z, K,,=k3/k_, and mechanism. Apparently separable behavior
K,, = k,/k_.‘. Solving for OA and B, from eqs (4) and only occurs when the surface coverage of ad-
(5) results in p being given by sorbed reactants is very high or very low due to
p asymptotically approaching a limiting value.
@a ODP # 0) A mechanism of this type has-been examined by
p = 8,0,(@, = 0) Petersen and Pacheco (1984).
 On the separability of catalyst activity and kinetic behavior 1277

(3) All other mechanisms are type 3. Activity and

kinetics are effectively separable for type 3
mechanisms when,, for the entire range of oper- 1.6
ating conditions considered, there is a single 3- 0
1.5
rate-controlling step in the mechanism (surface L
reaction, adsorption etc.). Nonseparability is a
c
rT 1.2
direct consequence of the lack of such a step. z
The vast majority of mechanisms are type 3. e 0.9
Ei
Also included in this group are reaction systems
where products can be produced by two or s- 0.6

more foutes (e.g. parallel Eley-Rideal and z a.3

Langmuir-Hinshelwood reaction steps).
0.0

When examining mechanisms, all surface species must 0.60

be considered, even species which do not take part in
0.55
any reactions, but only interact with the surface a
through adsorption and desorption processes. This 0.50

classification indicates an approach which can be used 0.45

to explain reports of nonseparable behavior which
have appeared in the literature. This will be illustrated
by examples using data from two detailed experi-
CHzO1,or ECHJOHl x 0.1, mol/m’
mental studies of nonseparability (Bakshi and
GaGalas, 1975; &al and Butt, 1981). Fig. 1. Reaction rates and p for methanol dehydration on
fresh and poisoned silica-alumina (open symbols =fresh
catalyst; symbols = partially poisoned catalyst; circles
solid
=[HzO] = l.l(r1.24
mol/m’ with varying methanol con-
Example 1
centration; squares = [CH,OH] = 10.2 mol/m3 with varying
Bakshi and Gavalas (1975) examined the de- water concentration; 170°C reaction temperature; model
hydration of methanol on silica-alumina and made predictions using K 1 = 6.5 m3/mol, K, = 0.24 m’/mol, k,
measurements of p for a variety of conditions by using = 0.011 mol/h g-cat, K, , = 11, K, = 5 m3/mol, tip = 0.63).
a fresh and a poisoned catalyst (n-butylamine was
used as the poison). Their data [from Bakshi (1975)] is
shown in Fig. 1, where it is seen that, for a constant
methanol concentration, p decreases as the water where A and B represent acid and basic sites, respect-
concentration is increased (squares), and that, for a ively. To simplify the analysis, the following assump-
constant water concentration, p is approximately in- tions are made: steps (M2-2) and (M2-5) are at equilib-
dependent of the methanol concentration (circles). rium; steps (M2-3) and (M2-4) are irreversible; step
Bakshi and Gavalas (1975) did not propose a mech- (M2-4) is very fast relative to steps (M2-3) and (M2-1);
anism for methanol dehydration. Instead, they empiri- all A sites are energetically uniform (also true for B
cally described their data by using a rate function of sites); the total number of sites of type A is equal to
the form that of type B; and the poison (n-butylamine) only
affects the type A sites. Using these assumptions in
k,K, ,/CCH,OHl
r= (9) conjunction with surface species balance equations
~+K,&zH,oH]+-K,[~,O]’ gives the rate of formation of ether:
The variation in p was accounted for by using two r=k 3 @CH,O5 CH,OH (10)
different sets of values for the rate constants in eq. (9).
However, it is also possible to account for variations in where QcnXOis determined from the solution of (note
p without changing the values of rateconstants for the OcHIO= &, due to the assumptions)
fresh and the poisoned catalysts, but instead by Kt CCH,OHl
utilizing a reaction mechanism which intrinsically Gi,O
1+KsCHzOl
gives rise tp nonseparability. For example, KnSzinger
et al. (1973) examined several mechanisms for this
reaction, &e of which is as follows (mechanism 2):
CH,OH(g)+A+B=CH,O-A+H-B (M2- 1)
+(K,, - l)K,[CH,OH] - 1
I
CH,OH(g) + E%=CH,OH-B (M2-2)

CH,O-A+CH,OH-B+(CH,),O(g)+OH-A+B
(M2-3)
OH-A + H-B + H,O-A + B (M2-4)
(11)
H,O(g) + A=+H,O-A (M2-5)
1278 DAVID T. LYNCH and GERHARD EMIG

subsequently
with SCH,OH found from 23

CHsOH = (12)
1 + K, [CH,OH] 22

where K 1, K, and K,, are as in mechanism 1, and

K,=k,/k_,.
21
Values of the parameters were estimated by non-
linear regression using the rate data in Fig. la, and the
model predictions are shown in Fig. la as solid (water
20
concentration varied) and dashed lines (methanol
varied). It is seen in Fig. 1b that this simplified model,
using a single set of parameter values, can adequately 19
describe the experimentally observed values of p. This 0.16 b
is possible because mechanism 2 is a type 3 mechan- -i=--.._
0.12
ism, which for the chosen parameter values has a shift %---._
in the rate-controlling step from surface reaction (M2- 0.08
3) to adsorption (M2-1) as the water concentration a.04
(and thus the fractional coverage of water on the A
0.00
sites) is varied. 2.20 2.25 2.90 2.35 2.40 2.45 2.60
While even better agreement with the rate data
would be possibIy by relaxing one or more of the (Temperature)-’ x 1000, K-’
assumptions (with more parameters needed), this is
not warranted given the accuracy of the data (see p Fig. 2. Reaction rates and p for benzene hydrogenation on
fresh and poisoned (two levels) supported nickel [triangles
values for methanol variation). In addition, the pur-
=fresh catalyst; squares =“16%” activity; circles =“6%”
pose of this example is not so much to describe activity; average reactant pressures: P, = 38 tom, P,, = 817,
methanol dehydration kinetics as to illustrate that 770 and 721 torr for fresh, “16%” and “6%” catalysts,
nonseparability can be readily described by use of an respectively (rates in mol/s g-cat); model. predictions using
K; =3.5x 10-h torr-‘, Q,/R=42OOK, K’$=lO-‘torr-‘,
elementary-step mechanism employing only a single
QJR = Q K k; = 10” mol/s g-cat, E,/R=4500 K, K;*
set of values for the kinetic parameters.
=6000, 8,(16%)=0.68, 0,(6%)=0,81].

Example 2
mechanism is type 1, and variations in p due to
&al and Butt (1981) examined the hydrogenation
operating conditions can never be described by this
of benzene on a supported nickel catalyst_ Their data
mechanism when onIy a single set of parameters is
[from &al (1981)] is shown in Fig. 2a, where for the
used. Thus, the observation of nonconstant values of
sake of consistency the form of the axes is the same as
p leads to the conclusion that mechanism 3 is not
that used by &al and Butt (1981). In Fig. 2b it is seen
consistent with the data in Fig. 2.
that p increases as the tempemture increases (benzene
In a recent study, ZrnEeviC and RuGi: (1988) pro-
pressure is constant; hydrogen pressure is approxi-
posed an alternate mechanism for the hydrogenation
mately constant). &al and Butt found that their rate
of benizene on nickel given by (mechanism 4)
data was adequately described by a rat& function of
the form C,H,(g) + S+C,H,-S (M4- 1)
H2(g) + 2S=2H-S (M4-2)
(13)
H-S+C,H,,.-S-+&H,+,-Si-S (n=O, 1, 2, 3, 4)
This was derived from a mechanism in which it was (M4-3)
assumed that an Elcy-Ridcal type reaction occurs
H-S+C,H,1-S+C6H,2(g)+2S. (M4-4)
involving a gas-phase hydrogen molecule and a Z-
bonded benzene complex (Kehoe and Butt, 1972), By assuming that the surface reaction between ad-
according to the steps (mechanism 3) sorbed benzene and adsorbed hydrogen is rate-con-
trolling [step (M4-3) with n =0] they arrived at the
C,H,(g)+ S+C,H,-S (M3-1)
rate function
H,(g)+ C,H,-S-+C,H,-S (M3-2)
k,K, .,k f&k,
H,(g)+C,HB-S-+C,H,o-S (M3-3) (14)
‘=(l +K,P,+,/K,P,,)2
HZ(g)+Cl,H,.-Sj~,H,,(g)+S. (M3-4)
which gave the best description of their data. While
In order to describe the reaction rates at the three discrimination between rival mechanisms is normally
levels of activity, three different sets of parameter based on statistical considerations, qualitative sup-
values were used (12 parameters in total). Three sets of port for mechanism 4 was provided by the authors by
parameter values were necessary because, in the con- observing the variation of activity with respect to time
text of the classification system employed herein, this during continuous poisoning of the catalyst (constant
 On the separability of catalyst activity and kinetic behavior 1279

concentration of poison in the reactor feed stream). when the catalyst can be deactivated to fixed levels,
From the development for mechanism 1, it is clear that with constant activity at each level.
if the assumption of a single rate-controlling step is
removed, then mechanism 4 should be capable of Acknowlrdgrmenf-The sponsorship of this work by the
describing the variation of p with respect to tempera- Alexander van Humboldt-Stiftung (research fellowship for
D.T.L.) ix grAtefully acknowledged.
ture shown in Fig. 2b because this mechanism is
type 3. This would provide additional support for
NOTATION
mechanism 4 over mechanism 3. If it is assumed that
the surface is energetically uniform, with step (M4-2) a catalyst activity
at equilibrium, and with only adsorbed hydrogen and A reactant species (mechanism l), or acid site
benzene present on the surface in appreciable quan- (mechanism 2)
tities [step (M4-3) with n=O is much slower than the B reactant species (mechanism l), or basic site
n > 0 steps], then the rate of benzene hydrogenation is (mechanism 2)
given by bulk-phase concentration
: product species
r=k,tY,t?, (15) activation energy
K/R
where Bs is determined from the solution of ki adsorption, or surface reaction, rate con-
stant
O%, L &W’H, -Q,jl +~,~,+C~31(1-~,) k_i desorption rate constant
Ki ratio of adsorption to desorption rate con-
+lIJK~P”~}+K,P,(l-~O,)=O (16)
stant
with 8, subsequently found from Kij ratio of surface rate constant to desorption
rate constant
QiIR heat of adsorption
r overall rate of reaction
ri intrinsic rate of reaction
where K,=K;eQ’IRT, K~=K;~Q~IRT, k,=k”,emE’IRT
cata1ys.t activity
and K,, = KO,, eCQ1pEJ)‘RT. The values of the par- ; catalyst site for adsorption
ameters were estimated using nonlinear regression, T bulk-phase temperature
and the predictions from eqs (15j(17) are shown iq
Fig. 2 as solid’lines. It is seen that excellent agreement Greek letters
is possible and that temperature-dependent values of p parameters [eqs (6)-(S)]
I> B
are predicted. Thus, it is possible to discriminate fractional surface coverage of reactant A
0,
between mechanisms 3 and 4 based on the structural (mechanism 1)
characteristics of the mechanisms (type 1. vs type 3) fractional surface coverage of reactant B or
8,
instead of based on the more commonly employed benzene (mechanism 4)
statistical considerations. The possibility of this type fractional surface coverage of hydrogen
0,
of structural model discrimination should be con- (mechanism 4)
sidered when planning experiments for examining fractional surface coverage of poison (all
0,
reaction rate behavior, because the current state-of- mechanisms)
the-art of kinetic model development leaves a great 0 CHlO fractional surface coverage of methoxide
deal to be desired (Berty, 1988). radicals on acid sites (mechanism 2)
5CH,OH fractional surface coverage of methanol on
CONCLUSIONS basic sites (mechanism 2)
It has b&en shown that even for energetically uni- 5H fractional surface coverage of hydrogen on
form (ideal) surfaces the routine assumption of separ- basic sites (mechanism 2)
ability of kinetics and activity should be re-examined. P measure of separability
In particular, complete separability is only guaranteed
for a very restricted class of mechanisms (type 1). REFERENCES
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