Coke poisoning effect on xyl ene

isomerization and on n- hexane cracki ng

over H-offretite
Mi c he l Gui s ne t a nd Gi l l e s Bo u r d i l l o n
Laboratoire, Associg au C~ RS 350, Catalyse Organique, UER Sciences, 40, A venue du Recteur Pineau,
86022 Poitiers Cedex, France
a nd Cl aude Gu e g u e n
Centre de Recherche E l f Solaize, B. P. 32, 69360 Saint Symphorien d'Ozon, France
(Received 12June 1984)
Whi l e the sensi ti vi ty to coke of t he reactions on Y zeolite depends onl y on t he acid strength of t he active
centres, on offretite, it mai nl y depends on t he accessibility of the reactants to t he acid centres.
Keywords: H-offretite; xylene isomerization; n-hexane cracking; coke toxicity; site accessibility
It is currently admi t t ed that the stronger the acid
centres of a zeolite, the more sensitive to coke
poisoning they will be. Thi s allows us to explain why
the activity of an H- Y zeolite decreases with its coke
content all the more rapidly than the reaction studied
demands stronger acid centres. Thus, Figure 1 shows
that n-hexane cracking is definitely more poisoned by
coke than m-xylene isomerization. Thi s is due to the
fact that n-hexane cracking requires very st rong acid
centres, sin'ce they must be capabl e of retaining the
pyridine adsorbed at t emperat ures above 500C I
whereas the isomerization of m-xylene demands
weaker acid sites 2. On the contrary, over an
H-offretite (formula K0.1 H4.0(AIO~)4.1(SiO2)13.9, ori-
gin Grace Davi dson), coke toxicity is great er in
m-xylene isomerization than in n-hexane cracking
(Figure 2). Hence the strength of the active centres is
not the det ermi ni ng factor in this toxicity.
Nor is this difference in toxicity related to the origin
of the coke: what ever be the react ant --m-xyl ene or
n-hexane---a 1 wt % deposit of coke eliminates >80%
of the activity of offretite in the isomerization of
m-xylene and only 30% in n-hexane cracking. Thus
with 1 wt % of coke formed duri ng m-xylene
transformation, offretite has an activity for n-hexane
cracking equal to 70% of the activity of the fresh
catalyst i.e. identical to the one found for a 1% coke
deposit duri ng n-hexane cracking (Figure 2).
The difference in sensitivity to coke of the two
reactions is pr obabl y due to the porous st ruct ure of
offretite. Indeed, offretite is a zeolit.e presenting rec-
tilinear, cylindrical channels (d o 6.3 A) i nt ercommuni -
cating by gmelinite cages (elliptical openings 3.6 x
5.2 A) 3. The channels are large enough to allow the
diffusion of xylenes whereas the gmelinites let the
n-hexane but not the xylenes to penetrate. The porous
network of offretite is therefore tridimensional for
n-hexane and unidimensional for bulkier molecules
such as xylenes. Acid centres are situated in the
channels and in the gmelinite cages. Because of its
size, m-xylene can only react in the channels whereas
n-hexane can crack j ust as well in the gmelinite cages
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308 ZE O L I T E S , 1984, Vo l 4, O c to ber
as in the channels. Coke is formed preferably in the
channels poisoning their acid centres by adsorpt i on or
again blocking the channel thus preventing the
molecules from reaching the acid centres. Thi s
explains the very great sensitivity to coke of m-xylene
isomerization. On the ot her hand coke does not
prevent the circulation of n-hexane through the
gmelinite cages and this hydr ocar bon could therefore
transform itself on the acid centres of the channels
bet ween two plugs of coke or again on the acid centres
in the gmelinite cages. In agreement with this
interpretation it can be noted that in the product s of
the n-hexane cracking the branched molecules dis-
0 . 8
0 . 6
0 . 4
O.2
I I I I I I I I I I I
1 5 10
% c o k e
Figure 1 Change in the activity of H- Y zeolite as a f unct i on of its
percentage of coke. AR: ratio of the activities of the coke-poisoned and
the fresh catalysts. Operating conditions: Dynamic reactor, t = 350C;
PN2 = 90 KPa; Phvd,o~,bo. = 10 KPa
0 o ~
O.6
OA
! I I
1 5 8
% c o k e
Figure 2 Change in the activity of H-offretite as a function of its
percentage of coke. AR: ratio of the activities of the coke-poisoned and
the fresh catalysts. Operating conditions: Dynamic reactor, t = 350C;
pN= = 90 PKa; Phvdrocarbo, = 10 KPa. (&)Coke deposi t ed duri ng m-xyl ene
transformation
Short Papers
appear completely when the coke cont ent equal s 2%
i.e. when the activity of offretite for m-xylene
isomerization is totally suppressed (Figure.2).
CONCL US I ON
On H-offretite the sensitivity to coke of reactions
involving react ant s such as n-hexane for which the
porous net work can be considered as tridimensional is
definitely weaker t han for the ot her reactions such as
xylene isomerization.
REFERENCES
1 Bourdi l l on, G., Gueguen, C. and Gui snet, M., to be published
2 Jacobs, P. A. ' Carboni ogeni c Act i vi t y of Zeol i tes' , El sevi er Amst er -
dam, 1977, p. 168
3 Csicsery, S. M. 'Zeolite Chemistry and Catalysis' (Ed. J. A. Rabo), ACS
Monograph 171, p. 668, Amer i can Chemical Society, Washington,
1976
Defi ni ti on of a zeol i t e
J. v . Smi t h
Department of Geophysical Sciences, The University of Chicago, Chicago, Illinois 60637, USA
(Received 20June, 1984)
Quot a t i ons f r o m t h e l i t er at ur e ar e gi v e n t o pr ovi de t he basi s f o r di scussi on of t h e t e r ms z eol i t e,
mo l e c u l a r si eve, i sost r uct ur al ( i sot ypi c) , h o me o t y p i c , s i mp l e a na l og, coupl ed anal og, st uf f ed
der i vat i ve. Unl ess an i nt e r na t i ona l c o mmi s s i o n r ul es o t h e r wi s e , i t is suggest ed t h a t t he t e r m z eol i t e be
used in its hi st or i cal cont ext : in br i ef , i t is an a l umi nos i l i c a t e wh o s e open t e t r a h e d r a l f r a me w o r k a l l o ws
i on e x c ha nge and r ever si bl e d e h y d r a t i o n , T h e t e r ms z eol i t e and mo l e c u l a r si eve ar e not s y n o n y mo u s .
Li ebau' s proposal I t hat the traditional definition of a
zeolite be modified has not been discussed and
approved by i nt ernat i onal commissions on nomencla-
ture. The following information is present ed as a basis
for discussion.
Breck 2 st at ed t hat "t he most i mport ant mol ecul ar
sieve effects are shown by the dehydr at ed crystalline
, , 3
zeolites, and listed McBai n as the originator of the
term molecular sieve. Breck further st at ed "zeolites are
crystalline, hydrat ed aluminosilicates of group I and
group II elements*, in particular, sodi um, potassium,
magnesium, calcium, st ront i um and bari um. (*As
formed in nat ure or synthesized. Hi gher pol yval ent
ions, e.g., rare earths, are readily i nt roduced by cation
exchange.) St ruct ural l y the zeolites are ' framework'
aluminosilicates which are based on an infinitely
extending three-dimensional net work of AIO4 and
SiO4 t et rahedra linked to each ot her by sharing all of
the oxygens. Zeolites may be represent ed by the
empirical formula:
M2/ , O. AI20 3. x SiO2. y H2 0
In this oxide formula, x is generally equal to or great er
t han 2 since AIO4 t et rahedra are j oi ned only to SiO4
tetrahedra, n is the cation valence. The framework
contains channels and i nt erconnect ed voids whi ch are
occupied by the cation and wat er molecules. The
cations are qui t e mobile and may usually be
exchanged, to varyi ng degrees, by ot her cations.
Intracrystalline ' zeolite' wat er in many zeolites is
removed cont i nuousl y and reversibly. In many ot her
zeolites, mineral and synthetic, cation exchange or
dehydrat i on may pr oduce st ruct ural changes in the
framework. In some synt het i c zeolites, al umi num
cations may be subst i t ut ed by gallium ions and silicon
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