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@ 1991 IUPAC
MANUAL ON CATALYST
CHARACTERIZATION
(Recommendations 1991)
Memberships of the Commission and Subcommittee during the period (1983-91) the report was prepared were as
follows:
*Chairman: 1983-91 K. S. W. Sing (UK); Vice Chairman: 1983-87 J. Haber (Poland); 1987-91 J. H. Block (FRG);
Secretary: 1983-85 E. Wolfram (Hungary); 1985-91 B. Vincent (UK); Titular Members: J. Czarnecki (Poland;
1989-91); B. Delmon (Belgium; 1989-91); P. C. Gravelle (France; 1985-89); J. Ralston (Australia; 1987-91); J.
RouquBrol (France; 1987-91); P. J. Stenius (Sweden; 1983-89); L. Ter-Minassian-Saraga (France; 1983-87);
Associate Members: J. B. Butt (USA; 1987-91); N. V. Churaev (USSR; 1983-87); J. Czarnecki (Poland; 1987-
89); B. Delmon (Belgium; 1987-89); D. Fairhurst (USA; 1987-91); P. C. Gravelle (France; 1983-85); J. W.
Hightower (USA; 1983-87); R. J. Hunter (Australia; 1983-87); H. N. W. Lekkerkerker (Netherlands; 1985-89);
A. J. G. Moroto (Argentina; 1983-91); M. Misono (Japan; 1989-91); G. I. Panov (USSR; 1989-91); P. Pendleton
(USA; 1989-91); D. Platikanov (Bulgaria; 1987-91); J. RouquBrol (France; 1983-87); P. B. Wells (UK; 1983-87);
National Representatives: G. F. Froment (Belgium; 1983-91); I. G. Ionescu (Brazil; 1983-85); L. A. Petrov
(Bulgaria; 1987-91): S. G. Mason (Canada; 1983-87); C. W. Fairbridge (Canada; 1987-91); A. Weiss (FRG; 1983-
87); G. Lagaly (FRG; 1987-89); G. H. Findenegg (FRG; 1989-91); K. Meyer (GDR; 1983-87); G. ohlmann
(GDR; 1987-91); L. G. Nagy (Hungary; 1983-91); J. C. Kuriacose (India; 1983-85); S. R. Sivaraja Iyer (India;
1985-89); D. K. Chattoraj (India; 1989-91); A. S. Kertes (Israel; 1983-85); J. Manassen (Israel; 1985-91); S.
Ardizzone (Italy; 1989-91); A. Kitshara (Japan; 1983-85); M. Misono (Japan; 1985-89); T. Kunitake (Japan;
1989-91); M. S. Suwandi (Malaysia; 198491); J. Lyklema (Netherlands; 1983-91); J. Haber (Poland; 1987-91);
M. Brotas (Portugal; 1985-91); H. Chon (Republic of Korea; 1989-91); M. S. Scurrell (RSA; 1989-91); J. A.
Pajares (Spain; 1983-91); H.-F. Eicke (Switzerland; 1985-91); S. Peker (Turkey; 1985-91); K. R. Kutsenogii
(USSR; 1989-91); D. H. Everett (UK; 1983-91); C. J. Powell (USA; 1985-89); S. MilonjiC (Yugoslavia; 1989-91).
tchairman: 1983-91 J. Haber (Poland); Secretary: 1983-91 J. H. Block (FRG); Members: L. Berlnek (Czecho-
slovakia; 1985-91); R. Burch (UK; 1985-91); J. B. Butt (USA; 1987-91); B. Delmon (Belgium; 1985-91); G. F.
Froment (Belgium; 1983-85); P. C. Gravelle (France; 1983-91); R. S. Hansen (USA; 1983-85); R. A. W. Haul
(FRG; 1983-87); J. W. Hightower (USA; 1983-85); C. S. McKee (UK; 1985-91); M. Misono (Japan; 1985-91);
J. A. Pajares (Spain; 1983-91); G. I. Panov (USSR; 1985-91); L. Riekert (FRG; 1983-91); M. W. Roberts (UK;
1983-85): K. S. W. Sing (UK: 1983-91); K. Tamaru (Japan; 1983-91); J. C. Vedrine (France; 1985-91); P. B.
Wells (UK; 1983-87).
~ ~~
Republication of this report is permitted without the need for formal IUPAC permission on condition that an
acknowledgement, with full reference together with IUPAC copyright symbol (0 1991 IUPAC), is printed.
Publication of a translation into another language is subject to the additional condition of prior approval from the
relevant IUPAC National Adhering Organization.
Manual on catalyst characterization
(Recommendations 1991)
CONTENTS
1. INTRODUCTION 1229
1. INTRODUCTION
This manual h a s been prepared by t h e Commission o n Colloid and S u r f a c e
Chemistry including C a t a l y s i s o f t h e I U P A C . I t results, from t h e g e n e r a l
feeling among surface and c a t a l y s i s c h e m i s t s both f r o m academia and industry
that t h e rapid increase o f k n o w l e d g e in s c i e n c e of c a t a l y s i s a n d t h e better
understanding of t h e mechanism o f c a t a l y t i c processes i s n o t accompanied by
the development of the appropriate scientific language. Many t e r m s , widely
used i n t h e literature, r e m a i n vague and undefined. T h u s , t h e S u b c o m m i t t e e o n
Catalysis w a s created with t h e task o f preparing a c a t a l y s t c h a r a c t e r i z a t i o n
c h a r t , listing all parameters which should be specified i n o r d e r to obtain
a f u l l description of a c a t a l y s t , and o f formulating t h e d e f i n i t i o n s o f t h e s e
parameters a s well a s recommendations concerning t h e terminology.
The p,resent manual i s based o n t h e s a m e g e n e r a l principles a s t h o s e used i n
the Manual o f S y m b o l s and Terminology f o r Physicochemical Q u a n t i t i e s and
Units' o f the Commission o n S y m b o l s , Terminology and U n i t s of t h e Division o f
P h y s i c a l C h e m i s t r y , D e f i n i t i o n s , Terminology ayd S y m b o l s in Colloid and
S u r f a c e Chemistry o f . t h e Commission o n Colloid and S u r f a c e C h e m i s t r y ,
Appendix I 1 P a r t I D e f i n i t i o n s , Terminology and S y m b o l s in Colloid and Surface
Chemistry , P a r t I 1 Heterogeneous Catalysis , and Recommendations i n Reporting
Physisorption Data for Gas/Solid S y s t e m s . (ref. 1-3)
S i n c e t h e present proposals should b e considered a s o n e o f t h e s u b - s e t s o f
the t e r m s and s y m b o l s o f physical c h e m i s t r y , t h e general p r i n c i p l e s a r e not
repeated h e r e . (see Note a )
This manual provides d e f i n i t i o n s and r e c o m m e n d a t i o n s concerning t h e terminology
o f c a t a l y s i s . It should b e read in conjunctio? with t h e Manual o f M e t h o d s
and Procedures f o r Catalyst Characterization which p r o v i d e s d e t a i l s and
recommendations concerning t h e experimental methods used i n c a t a l y s i s .
2. CATALYST FORMULATION AND METHODS OF ITS PREPARATION
2.1 Methods of preparation
A + D = A D = A - + D+
t h e s t e a d y s t a t e , when t h e c a t a l y s t i s n e i t h e r a n e t s o u r c e n o r a s i n k o f
m a t e r i a l . The c r i t e r i o n u s e d t o d e f i n e t h e s t e a d y s t a t e s h o u l d b e s t a t e d .
Q u a n t i t a t i v e d e s c r i p t i o n o f c a t a l y t i c p r o p e r t i e s r e q u i r e s t h a t t h e system
under c o n s i d e r a t i o n be unambiguously d e s c r i b e d with respect t o system
b o u n d a r i e s (mass o f c a t a l y s t m , a r e a o f c a t a l y t i c s u r f a c e A , or v o l u m e o f
p o r o u s c a t a l y t i c p a r t i c l e V )-‘and c o n d i t i o n s s u c h as c o m p o s i % i o n , p r e s s u r e ,
t e m p e r a t u r e , p r e v a i l i n g at+ t h e boundary ( c o n t r o l v a r i a b l e s ) . A s e t o f d a t a
c h a r a c t e r i z i n g a c a t a l y s t must p e r m i t t h e p r e d i c t i o n o f m a t e r i a l b a l a n c e o f
t h e s y s t e m c o n t a i n i n g t h e c a t a l y s t a t s t e a d y s t a t e u n d e r a t l e a s t one s e t o f
c o n t r o l v a r i a b l e s . I t i s sometimes p o s s i b l e t o r e p r e s e n t a number of
e x p e r i m e n t a l o b s e r v a t i o n s by r a t e e q u a t i o n o r a set o f r a t e e q u a t i o n s which
may o r may n o t b e b a s e d o n a m e c h a n i s t i c m o d e l . The m o d e l h a s t o f u l f i l t h e
above c r i t e r i a w i t h i n a c e r t a i n r a n g e o f v a l i d i t y w h i c h s h o u l d b e i n d i c a t e d .
The c a t a l y t i c s y s t e m s h o u l d b e c h a r a c t e r i z e d w i t h r e s p e c t t o t h e r a t e o f
c h e m i c a l change ( a c t i v i t y ) and w i t h r e s p e c t t o product composition ( s e l e c t i v i t y ) .
5.2.1 Reaction r a t e
We d i s t i n g u i s h i n t e g r a l a n d d i f f e r e n t i a l characteristics of catalytic
p r o p e r t i e s . One o f t h e i n t e g r a l c h a r a c t e r i s t i c s i s t h e e x t e n t o f r e a c t i o n 15.
G e n e r a l l y , a n y c h e m i c a l r e a c t i o n , w h e t h e r o v e r a l l or an e l e m e n t a r y s t e p , c a n
be r e p r e s e n t e d b y a s t o i c h i o m e t r i c e q u a t i o n :
where V i s t h e s t o i c h i o m e t r i c c o e f f i c i e n t o f component B . , t a k e n p o s i t i v e
when Bi-i i s a p r o d u c t a n d n e g a t i v e when i t i s a r e a c t a n t 4 The c h e m i c a l
c h a n g e - o c c u r r i n g i n t h e c o u r s e o f t h e r e a c t i o n may b e d e s c r i b e d b y % ( i n m o l ) :
ci - n.
-1 0
E=
- -
Vi
-
-A
where q oa n d ci a r e t h e a m o u n t s o f s u b s t a n c e Bi ( i n m o l e s ) a t t i m e z e r o
and a t - a n y - t i m e , r e s p e c t i v e l y . I t i s an -extensive q u a n t i t y a t t a i n e d
under s p e c i f i e d c o n d i t i o n s .
An a l t e r n a t i v e e x p r e s s i o n i s i t s d i m e n s i o n l e s s f o r m , h a v i n g a v a l u e b e t w e e n
z e r o a n d u n i t y , c a l l e d f r a c t i o n a l c o n v e r s i o n or d e g r e e o f c o n v e r s i o n .
The d r a w b a c k o f i n t e g r a l c h a r a c t e r i s t i c s s u c h a s e x t e n t o f r e a c t i o n or d e g r e e
o f c o n v e r s i o n i s t h a t v e r y many c o n t r o l v a r i a b l e s s u c h a s t h e r e a c t o r t y p e ,
f e e d c o m p o s i t i o n , t i m e , t e m p e r a t u r e , e t c . , i n f l u e n c e t h e v a l u e s o b t a i n e d and
have t o be s t a n d a r d i z e d . Moreover, w i t h h i g h c o n v e r s i o n , a g r e a t d i f f e r e n c e
i n c a t a l y t i c a c t i v i t y u s u a l l y leads t o only s m a l l differences i n t h e conversion
values.
A d i f f e r e n t i a l c h a r a c t e r i s t i c w h i c h demands a l o w e r d e g r e e o f s t a n d a r d i z a t i o n
i s t h e r e a c t i o n r a t e . The r a t e o f a c h e m i c a l r e a c t i o n w i t h r e s p e c t t o compound
B a t a g i v e n p o i n t i s d e f i n e d as t h e r a t e o f f o r m a t i o n o f B i n moles p e r u n i t
t i m e p e r u n i t volume. I t c a n n o t be measured d i r e c t l y and i s d e t e r m i n e d f r o m
t h e r a t e s o f c h a n g e o f some o b s e r v a b l e q u a n t i t i e s s u c h a s t h e amount o f
s u b s t a n c e , c o n c e n t r a t i o n , p a r t i a l p r e s s u r e , w h i c h a r e s u b j e c t t o measurements.
R e a c t i o n r a t e s a r e o b t a i n e d f r o m o b s e r v a b l e q u a n t i t i e s by use of the
c o n s e r v a t i o n e q u a t i o n s r e s u l t i n g f r o m t h e mass balance for t h e g i v e n r e a c t o r t y p e .
-
t = time
Manual on catalyst characterization (Recommendations 1991) 1241
-
k = -
A.exp[-E/(O)]
where 4 is the pre-exponential factor and i s the activation energy. Where
an overallcatalytic .reaction o b e y s the Arrhenius equation o v e r a certain range
o f temperatures t h e experimentally determined energy i s a n apparent activation
energy.
A r a t e equation in t e r m s o f t h e local composition o f reacting fluid i n contact
with t h e surface o f the catalvticallv active material may be called t h e
"intrinsic" r a t e e q u a t i o n ; t h e c o e f f i c i e n t s in t h i s e q u a t i o n a r e "intrinsic"
r a t e coeffic,,;nts. The local concentrations of reactants and p r o d u c t s a t the
catalytic surface in general cannot b e observed and have to be inferred from
1242 COMMISSION ON COLLOID AND SURFACE CHEMISTRY INCLUDING CATALYSIS
n.
-1
(S.) = :
-1 R
- 1 n-
i
when t h e feed stream consist o f t h e s e t o f reactants B .
An alternative expression i s t h e ratio between the mass o f P i in t h e products
and t h e total mass o f products generated from 8 . -
The y i e l d ( Y ) o f product P i i s defined as:
-
Amount o f B converted into P i Number o f molecules o f B converted into P i
-
Y =j
-
as due to reaction with Is: restriction of physical access due to formation
of a (semi) impervious layer of &.
The IS may (i) be present in the tants as impurities, (ii) come from
other sources (equipment, etc.) o r be formed during the course of the
reaction (by transformation of intermediary o r final products, etc.).
Ideally, the characterization of catalysts with respect to inhibition should
involve 3 types of information:
1. nature of the & acting on the catalyst,
2 . adequate relationship between the quantity of IS and catalytic properties,
3 . time-dependent effects on activity, selectivity, etc., due to the presence,
or a modification of concentration, of & (decreases of catalytic activity
with time, total o r partial recovery of catalytic properties after removal
of & from the feed, etc.).
-
IS may be classified into three categories:
Poisons (true poisons) are characterized by their propensity to attach very
strongly, by a truechemical bond (e.g. covalent) to the surface atoms or
ions constituting the catalytically active sites. Poisons act in minute
quantities. Typical poisons of metals are S, As, etc. In most cases, activity
and/or selectivity cannot be recovered without a drastic change in operating
conditions (most often a regeneration). Recovery, if at all, takes place very
slowly and/or only partially.
Inhibitors have a transient effect (inhibition). All catalytic properties can
be recovered after the supply of the inhibitor to the catalyst has been
stopped, without othel-wise changing the operating conditions. Inhibitors act
in minute quantities, have a reversible effect pi71 correspond to more or
less strong bonding.
Fouling agents, o r mechanical inhibitors are bound by neither covalent nor
other strong bonds to the active centres: the interaction is usually of the
van der Waals, H-bond, or sometimes ionic, type. They form protective layers
o r block pores, thus physically impeding access of reactants to the active
centres. The fouling agents causing real problems are those which have a long
standing effect and do not disappear spontaneously. Carbon deposits act,
partially or totally, this way. Other examples are vanadium and nickel sulfide
deposits in hydrotreating catalysts.
Fouling agents act in quantities equivalent to several layers spread over the
catalyst surface or to pore volume; they may according to different cases,
have a rapidly reversible, an only slowly reversible, o r an irreversible
effect .
5 . 5 . 2 Characterization of catalyst response to inhibitory substances
In principle, sensitivity to inhibition (by poisons, inhibitors o r fouling
agents) depends on the whole catalytic reaction system: nature of catalyst,
degree of ageing (in particular, nature and degree of poisoning, modification
of activity and selectivity by inhibition and fouling), operating conditions,
etc. Accordingly, the activity and selectivity of a catalytic reaction depends
on all the previous history of the catalyst.
Sensitivity to the deactivating influence of impurities, reaction products o r
intermediates is expressed in different ways depending on the category of
deactivating agent (poison, inhibitor, fouling agent).
5.5.2.1 Poisons
Sensitivity to poisons depends on:
-number of active centres in the catalyst: when it is small, the
catalyst may be inhibited by a small amount of poison;
-strength of adsorption of the poison on the active centres;
the weaker is the adsorption of poison, the lesser is the sensitivity
of the catalyst to poison;
-the effectiveness of adsorbed poison for inhibiting the catalytic
activity;
the latter decreases sometimes on adsorption of small amounts of
poison on active centres more than in proportion to the fraction of
active centres covered by the poison.
Manual on catalyst characterization (Recommendations 1991) 1245
REFERENCES