Académique Documents
Professionnel Documents
Culture Documents
Vol. .65
CATALYSIS AND
ADSORPTION BY
ZEOLITES
Proceedings of ZEOCAT 90, Leipzig, August 20-23, 1990
Editors
G. Ohlmann
Zenrralinsrirur fur Physikalische Chemie, Rudower Chaussee 5,
Berlin Adlershof, 0- 1 7 99 FRG
H. Pfeifer
Universirar Leipzig, Sekrion Physik, Linnhstrasse 5, Leipzig, 0-70 10 FRG
and
I?.Fricke
Zenrralinstirur fur Physikalische Chemie, Rudo wer Chaussee 5,
Berlin Adlershof, 0- 1 199 FRG
ISBN 0-444-89088-2
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or
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CONTENTS
Preface.........................................................XI
International Scientific Committee, National Organizing
Committee, Sponsors ........................................... XI11
INVITED LECTURES
SUBMITTED PAPERS
Catalvsis
Aciditv
PREFACE
ZEOCAT 90 - Leipzig
SI)onsors
AKZO Chemicals B.V.
BASF AG
BAYER AG
Chemie AG Wolfen-Bitterfeld
Degussa AG
Deutsche Shell AG
EXXON Chemical Holland-BCT
Hoechst AG
Intern. Zeolite Ass. (IZA)
Leuna-Werke AG
PCK AG Schwedt
PQ Corp.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 1
0 1991 Elsevier Science Publishers B.V.. Amsterdam
AbS1 R A L !
sed, by i n t e r a c t i o n w i t h t h e b r i d g e d h y d r o x y l groups, o r by u a r -
t i a l deaiumination.
i n t h i s paper we d e s c r i b e t h e combined e f f e c t o f h y d r o t h e r m a l
d e a l u m i n a t i o n and phosphorus m o d i f i c a t i o n on t h e s e l e c t i v i t i e s and
d e a c t i v a t i o n rimes i n t h e high-temperature MTO-reaction. F o r a l l
experiments t h e ZSM-5 type. template-free synthesized z e o l i t e
HS-30 o f Chemie AG B i t t e r f e l d , has been used. TPD o f ammonia, I R -
and :*1P--.27AI-MAS-NMR soectroscopy were employed t o g e t deeper
i n s i g h t i n t o t h e mechanism o f t h e z e o l i t e m o d i f i c a t i o n by o r t h o -
ptiosplioric a c i a . l h e work was p a r t o f a c o o p e r a t i o n w i t h t h e
Researcn and Uevelopment D i v i s i o n o f Leuna-Werke-AG.
f r e P a r o r i o n v t soimles
P e n t a s i l t y p e LSM-5 z e o l i t e (HS-30, Si/Al=19, Chemie AG B i t t e r -
t e l d ) i s c o n v e r t e d I n t o t h e H*-form by a f o u r t i m e s r e p e a t e d
t r e a t m e n t w i t h a 0 . 2 N so1.ution o f HN03 i n a s i m u l e b a t c h Proce-
d i i r e . For d e u l u s i n a t i o n . samples o f t h e H+-form a r e exposed t o a
stream o t a i r and steam (pwater.=90 kPa) a t 400, 410 and 700°C.
Framework aluminiirm ( A h ) i s determined u s i n g t h e ammonium exchon-
ge method. For p a r t i a l e x t r a c t i o n o f non-framework aluminium
t A 1 1 . i ~ ) torined d u r i n g deUlUminatiOn, samples a r e t r e a t e d w i t h 2 N
HN03 a t 105°C f o r t w o h o u r s . E x t r a c t e d aluminium was d e t e r m i n e d
o n a l y t i c a l l v i n the s o l u t i o n o f t h e e x t r a c t i n g agent. C a t a l y s t
p a r t i c l e s were oreoared by m i x i n q t h e HS-30 samples w i t h Aero-
sil-ZGO and water and subsequent e x t r u d i n g , t h e ready made e x t r u -
d a t e s (d = 1 t o 2 mm) c o n t a i n i n g 6 5 % by w e i g h t o t z e o l i t e . P-modi-
r i c a t i o n was c a r r i e d o u t by i m p r e g n a t i o n w i t h aqueous p h o s p h o r i c
a c i d . i h e c o n t e n t o f phosphorus f o r c a t a l y s t s based upon e x t r a c t e d
HS-30 was h e l a somewhat lower t a k i n g i n t o c o n s i d e r a t i o n t h e i r
di.minished c o n t e n t s o f t o t a l . alilminium. F i n a l l y c a t a l y s t samples
were c o n d i t i o n e d b y steaming a t 700°C f o r 1 h o u r .
Ammonium exchange
l h e H I - i o n s o t LSM-5 z e o l i t e s a r e exchanged by NH4*-ions by
treatment w i t h an aqueous s o l u t i o n o f an ammonium s a l t . F o r t h i s
Purpose t h e sample i s p l a c e d on a 64 s l a s t r i t (approx. 4s) and
exposed t o CI tiow o f 50u m l o t an aqueous 0,2 N NH4(CHaCOO) s o l u -
t i o n t o r b Iluurs a t /c) t o 80°C. A t t e r c a r e f u l washing, t h e c o n t e n t
4
o f ammonium i s d e t e r m i n e d by t h e K j e l d a h l method.
D e t e r m i n a t i o n o f ahasphorus i n o w ous s o l u t i o n s
Ihe suiiif d e v i c e a s i n t h e ammonium exchanse i s used t o a n a l y z e
phosphorus removed from P-modified samples by e l u t i o n w i t h h o t
w a t e r . Q u a n t i t a t i v e d e t e r m i n a t i o n o f t h e e x t r a c t e d Phosphorus i s
based on t h e p h o t o m e t r i c molvbdo-vanada-phosphoric a c i d method.
T R Soectroscooy
LSM-5 z r o l i t e samples a r e compacted t o t h i n s e l f s u p p o r t i n g
waTe1-s tiouohlu 7 mg/cmz) and p l a c e d i n a q u a r t z 1 R c e l l . The
worers o r e c u r c i n e a a t 400°C i n vacuo. A f t e r c o o l i n g t o 200°C,
p y r i o i n e vapour i s uailiitted i n t o t h e system f o r 30 m i n u t e s . A f t e r -
w u r ~ t s , t l i e c e l l 1 s degusbecl and evacuated t o e l i m i n u t e p h v s i s o r b e d
P v r i d l nf
Transmission s p e c t r a a r e r e c o r d e d i n t h e range from 4000 t o
3300 cm-' b o t h h e t o r e and a f t e r p y r i d i n e n d s o r p t i n n . u s i n g o
SDecord M 85 spectrometer o f C a r l Z e i s s Jena w i t h a 4 c m - l r e s o l u -
t ion.
Diffuse r e t l e c t a n c e s p e c t r a a r e r e c o r d e d w i t h t h e t - T - 1 H t e c h n i q u e
u s i n g u s p e c i a l aevice, t h e r e s o l u t i o n o f which i s 4 cm-I. The
z e o l i t e Powdei i s p r e t r e a t e d f o r t o u r h o u r s a t 450°C and a t
10- ' Po
L 7 A l- and P-MAS-NMK--measurement s
I h e NMK s p e c t r a were o b t a i n e d on a BRUCKER MSL4OO m u l t i n u c l e a r
spectronieter o p e r a t i n g a t u f i e l d o t 9 , 4 r w i t h a s t a n d a r d BRUCKER
d o u b l e - b e a r i n g MAS p r o b e , I h e z i r k o n i u o x i d e r o t o r s were spun near
5
La t a l v s i s
C a t a l y t i c experiments were c a r r i e d o u t i n a t u b u l a r f i x e d bed
r e a c t o r (6 = 12 mm) u s i n g a m i x t u r e o f methanol/Nz ( m o l e c u l a r
r a t i o = 1 : l ) as r e a c t i o n feea ( c o n d i t i o n s o f r e a c t i o n see t a b l e 1 ) .
Products were analyzed DY an o n - l i n e o p e r a t e d guscnromotogrophic
device C a l c u l a t i o n o f t h e c o n c e n t r n t i n n from a n a l v t i c a l d a t a i s
based on i n d i v i d u a l c a l i b r a t i o n o f t h e components
lABLE I : Parameters o f r e a c t i o n
- ~ _ _ ~
t enipe r a t u r e : 560°C
c o n c e n t r a t i o n o t methanol: 50 Val-%
c a t a l y s t volume: 12 m l
c a t a l y s t mass ( a v e r a g e ) : 5.b 9
teed t-are ( i n i x r u r e ) : 4 . 0 m l / s (Sir)
charge
GHSV ( m i x t u r e ) . 1200 m l / m l c a t I vs t *h
LHSV(methano1): 1 m 1/ml a t I I. *h
RESUL LS .MRDILSCUSSIQN
R e c e n t l y we have shown ( 2 0 ) , t h a t d e a l u r n i n a t i o n o f z e o l i t e
HS-30, used as c a t a l y s t i n t h e M'10-reaction a l t e r s t h e s e l e c t i v i -
t i e s o f l i g h t o l e f i n s and o f a r o m a t i c s i n a s i m i l a r way as was
found by Chans e t a 1 . ( 1 9 ) f o r ZSM-5 c a t a l y s t s s y n t h e s i z e d w i t h
v a r i o u s S ~ / A I F r a t i o s . f o r t h e r e a c t i o n c o n d i t i o n s chosen i n t h i s
worK t n e e t t e c t o t w r y i n g c a t a l y s t S i / A l F r o t i o on t h e s e l e c t i v i -
t i e s o t cZ-c4- o i e T i n s , L 6 - b - U r o l n a t i c s and methone as w e l l a s on
t h e d e a c t i v a t i o n t i m e i s demonstrated i n F i g . 1 . S e l e c t i v i t i e s o f
l i g h t o l e t i n s i n c r e a s e UD t o almost 70% wh,ile t h e f o r m a t i o n o f
a r o m a t i c s ond methane i s d i s t i n c t l v decreased UP t o c a t a l ~ s t
S i / A l F o r 2 6 8 . lhese changes a r e accompanied by ii inarked ~ r o l o i i ~ a -
t i o n o i t h e d e a c t i v a t i o n t i m e . As d e s c r i b e d i n a s e p a r a t e paper
( 7 0 ) a remarkable i n c r e a s e o f t h e d e a c t i v a t i o n t i m e may be n t t a i -
ilea by e x t r a c t i o n o t t h e non-tramework aluminium u t t e r s u i t i c i e n t -
IY l o n g d e a l u m i n a t i o n a t mediuin t e m p e r a t u r e s . F u r t h e r dealumina-
t i n n , however, does n o t r e s u l t i n a b e t t e r c a t a l v s t . O l e f i n s e l e c -
t i v i t i e s t e n d t o decrease a g a i n , t h e some h o l d s t r i i e o f t h e dent:--
t i v a t i . o n t i m e . W h i l e t h e s e l e c t i v i t i e s a t a r o m a t i c s a r e n o t sn
I0
6C
50
m
\
40
Y
r(
c
Y
r(
10
m
9
#
! 20
L
k
10
,so
'61 '9 6 268 102 1.25
F i g . l . E t t e c t o f d e a l u m i n a t i o n on p r o d u c t s e 1 e c : i v r t i e s and
O e a c t i v a t i o n t i m e compured w i t h u d d i t i o n a l phosphorus
inod1 t i c a t i o n
7
\
t i o n p r o d u c t s . Quite t h e o p p o s i t e Bo
b e h o v i o u r show t h e s e l e c t i v i t i e s
o f t h e a r o m a t i c s . They f a l l w i t h
g r o w i n g c o n t e n t o t phosphorus,
but agoin the catalysts with
7 0 . I yp!
\
67*57 ! I
d i T r e r e n t S i / A l F r a t i o s have d i f -
ferent levels o f s e l e c t i v i t i e s ,
M,
/,P$y
/
/. ,./
1'
ea
*/.,' ,/'
t h e lowest t o r
w i t h the highest
the c o t o l ~ s t s
degree o f de- 50.
.--__-.J
m-
-. ..
!'
I,'; . I
a l u m i n a t i o n . Here t h e samples
w i t h S i / A l i - = 3 3 0 e x h i b i t no exc:ep-
'i-330
I
\. I
\
40.
t i o n a l behoviour. [he suwr'es- I
S %
'
10 .
9 -
8 .
1 -
6 -
5 -
4 -
J -
2 .
1 -
I .'
0:5 i.0 1.5 2:O 2.5 IP 0.5 1.0 1,5 2.0 2.5 3.0 S P
p u r t i c u l n r i n the r e g i o n sx 4
between 1 . 5 and 2 . 0 % P .
i t i s g e n e r a l l y acceated ,,,- i4,
now. t h a t t h e higher *,
I
‘... ..__,
\
Si/A1=107
o l e t i n s a r e formed main- 1
’ -l
l v hv n l k v l n t i o n o f t h e
l o w e r ones w i t h m e t h a n o l
”-
rO‘
./’
I’
;.-*-. -__a
,/a
x Ethene
c) Propene
Butene
o r d i n i e t h ~ l e t h e r and t o 20. .”
P /d 0 C,-aliphatics
wme degree a l s o hv yi\x II
t h e i r o l i g o m c r i z a t i on.
tthene i s the primary
p r o d u c t o f t i r s t C-C-
lo- ---*--‘
\ ,!
ably also for crackinn. while catalyst ability for the alkvlation
o f oiefins by methanol is evidently less affected. lhis conclusion
i s supported by an experimerit with cofeeding of Propene to the
methanol stream durjng the MTO reaction. A higly dealuminated
cotalyst sample with very small concentration of strong acid Bran-
sted s i t e s , additionallv modified with 0.5% phosphorus was chosen
for this purpose. The most striking effect of cofeeded propene. as
f o l l o w s troin table 2, i s the distinct increase of methanol conver-
Products (% V o l . )
increusecl. I n e t a c t , t n a t t h i s i s v a l i d a l s o f o r t h e c o n c e n t r a t i o n
o f ethene i s i n d i c a t i v e o f t h e a t l e a s t p a r t l y m a i n t a i n e d c r a c k i n g
a c t i v i t y o t the catalyst.
To g e t deeper i n s i g h t i n t o t h e mechanism o f m o d i f i c a t i o n by
phosphorus t h e i n t l u e n c e
of growing amounts o f
phosphorus on t h e con- '*O
c e n t r a t i o n o f weaK and
0-3
strong a c i d s i t e s was A
s t u d i e d by NHS-TPD. I h e 7mC.6
IPD t r a c e s o f ammonia de- ,+
s o r p t i o n show characte-
r i s t i c a l l y o f ZSM-5 ( 2 2 )
8 OB:
t e n t i s accompanied bv a c o n t i n u o u s i n c r e n s e o f t h e c o n c e n t r a t i o n
o f weak a c i d s i t e s . r e a c h i n g w i t h 2 . 5 % P an even h j q h e r v a l u e t h a n
w i t h o u t phosphorus. l h i s complex dependency is a c l e a r i n d i c a t i o n
o t a change i n t h e n a t u r e o f weak a c i d s i t e s w i t h P - m o d i f i c a t i o n .
some o f them h e i n s removed, o t h e r s newlv c r e a t e d .
I h e f a c t t h a t P-content above 1 - 1 . 5 % t o r a l l S ~ / A I Fr a t i o s p r a c -
t i c a l l y t h e same c o n c e n t r u c i o n o f s t r o n g a c i d s i t e s is observeo
l e a d s t o t h e c o n c l u s i o n , t h a t t h e d i s t i n c t d i f i e r e n c e s i n Product
s e l e c t i v i t i e s . o b t a i n e d i n t h j s ranqe o f P - c o n t e n t s . s h o u l d he
due, a t l e a s t p a r t l y . t n t h e d i f f e r e n c e s i n n n t l r r e and c a n c e n t r a -
t i o n o f t h e w e a k a c i d s i t e s . rhus. weak a c i d s ' i t e s n t t h i s
high-temperature c o n d i t i o n s a r e l j k e l v t o p a r t i c i p o t e i n c a t a l v -
sis. O f course, an a d d i t i o n a l shape s e l e c t i v i t y e f f e c t caused bv
t n e growing amount o t P-compounds d e p o s i t e d i n s i d e t h e channels
cannot iie r u i e u o u t .
l h e q u e s t i o n i s now. how t h e decrease o f s t r o n g nnd weok a c i d
s i t e s caused by phosphorus m o d i f i c a t i o n can he e x o l a i n e d As n l -
ready mentioned. t h i s problem i s s t i l l d i s D u t e d . h u t t h e n i i t h n r s
OT most r e c e n t p u b l i c a t i o n s i n t e r o r e t t h i s e t f e c t e s s e n t i n l l v hv
d e a l u m i n a t i o n o t t h e z e o l i t e . I n case or a c n e m i c a l i n t e r a c t i o n
o f p h o s p h o r i c n c i d w i t h t h e b r i d g e d h v d r o x v l 4roiIPs as t h e a l t e r -
n a t i v e t o d e a l u m i n a t i o n , one would expect a c e r t n i n degree o r
reversibility. i n Fig./. t n e columns r e p r e s e n t a g a i n t h e sulil of
wenk and strong acid
s i t e s o f a non-dealuminn-
t e d z e o l i t e sample.
ThF! m o d i f i c a t i o n o f t h i s
sample w i t h 2 . 5 % P onrl
treatment for 1 hour
i n a He- stream n t 500 O L
causes a d i s t i n c t decrea-
se o t s t r o n q nc;.tl sites.
A T t e r e x t r a c r i o n o i phos-
p n o r i c a c i d w i t t i water u t
80 C'C t o r b h o u r s , now-
ever, t n e former concen-
t r a t i o n o f strong uciu
Fig.7.Changes o f a c i a s i t e s c o n c e n t r a - sites i s fully restorea.
t i o n of a P-modified s a m p l e ( D ~ ~ P ~ . o ConseqitPnt1.v) the rlis-
a f t e r various treatments (hatched onpearence o f s t r o n a a c i d
p a r t o t columns: c o n c e n t r a t i o n o f s i t e s has t o be under-
strong acid s i t e s ) . s t o o d as t h e r e s u l t o f
13
reversible chemicnl i n t e r a c t i o n o f p h o s p h o r i c a c i d w i t h t h e b r i g -
df*d h y d r o x v l q r o i t p s and cannot be due t o d e a l u m i n a t i o n o f t h e zeo-
. I i , t e . I f t h e P - m o d i f i e d sample p r i o r t o e x t r a c t i o n i s steamed f o r
4 hours o t 40u "i r e s p . t o r 0 , 5 hours a t 700 "C a f u r t h e r decrease
o r s t r o n g and weak a c i d s i t e s occurs (see F i g . 7 ) . The same e x t r a c -
t i o n pi-i.rr.edure, employed t o t h i s samples, a g a i n r e s t o r e s t h e aci.d
s i t e s b u t the o r i g i n o l c o n c e n t r a t i o n o f t h e s t r o n g a c i d s i t e s i s
nnt n t t n i n e r l l r r e v e r s i b l e changes. o b v i o u s l . . ~d e a l u m i n a t i o n , have
token olnce. I t tins t o b e noted, however, t h a t a f t e r steaminq i n
c o n t r a s t t o t h e i n e r e l y thermal o r e t r e a t m e n t i n He a t 500 " C . phos-
p h o r i c u c i a c o u l d be e x t r a c t e d o n l y by 89% and 60% r e s p e c t i v e l y .
l h e c ~ u e s t i o n o r i s e s us t o whether the Presence o t t h e p h o s p h o r i c
nLi.d 1.n the z e o l i i e channels i a v o u r s t h e process o f d e a l u m i n a t i o n
o r n o t . i h e ciiogront i n t-19.8. shows t h e c o n c e n t r a t i o n o t weak
and s t r o n g a c i d s i t e s o f
t w o HS-30 samples one un-
1.1
1.0
m o d i f i e d and t h e other
0.9 modified w i t h 2,5% P o f -
t e r steaming a t eqiinl.
- 0.8
70
30
20
10
bonded w i t h t h e non-framework a l i i m i n i u m
k u r t n e r s u p p o r t and a d d i t i o n a l i n f o r m a t i o n on t h e mechanism o f P-
m o d i t i c . a t l o n wete o b t a i n e d by means o f 1R- ond MAS-NMR-spectrosco-
PV I h e T i r s f two s p e c t r a i n F i g 10 a r r a n g e d one upon a n o t h e r ,
i l l u n t r n t e t h e e f f e c t o t P - m o d i f i c a t i o n ( 2 5% P, w i t h o u t steamiiiq)
3610
I
k i s . i U . I K - l r a n s l n i s s i o n s p e c t r a o f HS-30 samples o t t e r d i f f e r e n t
o r e t r e a t m e n t s . Kegion o t O H - s t r e t c h i n g f r e q u e n c i e s .
15
3740
P
at 120°C
37iC
/ :::5
-b-------L-
3900 3800 3700 3600 3500 3600
-- -'
I +steamed
lh at 700°C
?/Em
niiim. l h e i n t e n s e i n t e r a c t i o n w i t h t h e s t r o n g a c i d s i t e s and t h e
OH-QroUPS o r non-TrameworK a l u m i n i i l m can be concluded a l s o from
the d i f t u s e r e t t e c t a n c e IR-spectra presented i n F i g . 1 2 . A dealu-
minuted sample h l z , r u l l l i n e spectrum) shows t h e t y p i c a l bands
Tor o i l o b s e r v e a b l e OH-groups as a s s i g n e d b e f o r e . A f t e r m o d i f i c o -
t i o n w i t h 1 . 5 % P t h e c h a r a c t e r i s t i c bands o f t h e s t r o n g a c i d s i -
t?-, (361.0 cm-l) rind t h e A ~ N F - O H groitos ( 3 3 6 5 cm-') a r e s i q n i f i -
c n n t i v reduced. l n t e r e s t i n s l v t h i s spectrum r e v e a l s a s h o u l d e r o f
rJ twitid a t 3670 cm-' - a frequency r e g i o n , where P-OH-groups show
absorption. i h i s muy be c o n s i d e r e d as an i n d i c a t i o n o f t h e i r p r e -
sence.
Wh;le i t i s c l e a r trom t h e s e d a t a , t h a t p h o s p h o r i c a c i d r e a c t s
w i t h t h e b r i d a e u h v d r o x v l groups and t h e non-tramework a l u m i n i u n i
CIS w e l l . t h e i n t o r m a t i o n about t h e n n t u r e o f t h e p r o d u c t o f t h i s
i n t e r a c t i o i i remains r a t h e r D o o r . l h e r e f o r e t h e P - m o d i f i e d sarnolea
o d d i t i o n o l l v :;tiidie!d hv :I1P- and "'Al-MAS-NMR spectroscopv.
I h e :"P-MAS-NMR spectrum o f a d e a l u m i n a t e d P-modified sample
(spectram A i.n k i q . 1 3 ) e x h i b i t s a t l e a s t t h r e e d i f f e r e n t resonance
i i n e s . one o t them ( a t =1 ppm) corresponds t o t h e o r i g i n a l o r t h o -
ohosphorlr: o c i d . t h e second a t - 1 5 ppm r e p r e s e n t s c h e m i c a l s h i f t s
u s u a l l y o b t a i n e d t o r s h o r t c h a i n polyphasphates (241, and t h e r e -
inoinina l i . n e n t nboitt -;."-I opm corresoonds t o t h e range c h a r a c t e r i -
:;tic o f ~;IiiminiUr;i ahos- 3 r p - NMR ~ ~ -,
phiites ( 2 5 ) . Residues u l A
o r t h o u n o s p h o r i c o c i u and D95p1,6
A-A
dried a t 120% Y.:traotion (80.C)
snort c h a i n Doiyuhos-
phate s ~ e ~ i e fart? , remo-
vea by e x t r u c t i o r i w i t t i
spzctt'uin ils L ii n
wuter s k Shown
i g . 1 5 by
111 l h 100%
at eteame: ax'raction (80.C)
pnosphates, t h e pr'ouuct 71
0: i n t e r a c r i o n o r phos- k i q 13.="P-MAS-NMR s p e c t r a o t P - m o d i t l e d .
u h o r i c a c i d w i t h non- dealurninated samples o t t e r v a r l o t i r
f I ninework oluminium pretrmtments
r emoins
ITt h e sample i s steamed t o r 1 hour a t 100 " C (spectrum b) t h e
s i ~ n a i s a t 1 cliiu - 1 5 ppin d i s a p p e u r and new l i n e s a t -3Y and
-4b pplli appear U b v l o u s l y t h e p h o s p h o r i c anu POlyPhOSPhOt~lC a c i d
17
c o n d i t i o n s is u n l i k e l y t o occur,
D22P1 , 6 (>h/7W°C)
t n i s pnenonienoii i s i n u i c a t i v e TOI- o
very close i n t e r a c t i o n o r r w i t h A
AIP, causing a diStOrtiOn O T i t s , . . . . , . . . . I . . . . ,
c o n c e n t r a t i o n b u t a l s o t h e i r n a t u r e . Some i n c l i c a t i o n as t o t h i s
p o i n t was o b t a i n e d trom t h e temperature-programmed d e c o m p o s i t i o n
o f t h e NH-~*-exchanaed, P - m o d i f i e d samples.
c
h
,.
?
d
I
2M
F i n . l 5 . T e m p e r a t u r e - ~ r o g r a m m e d d e c o m p o s i t i o n o f an NH4+-exchanged
u n m o d i f i e d ( l e f t ) and P - m o d i f i e d somple.
D e a l u r i n a t i o n oT LSPI-5 t y p e HS-30 z e o l i t e bv h y d r o t h e r m a l t r e a t -
ment decreases t h e s t r o n g a c i d S i t e s and - c o n s e q u e n t l y i s osso-
c i a t e d w i t h a d i m i n i s h i n g o t c o t u l y t i c a c t i v i t y . C o n s e c u t i v e oro-
d u c t s o f t h e o l e f i n s a r e suppressed and t h e Cz-C4-olefin s e l e c t i -
v i t y i s r a i s e d . I t s v a l u e seems t o he l i m i t e d . however. t o about
b 5 X . M o d i t i c a t i o n of P r e v i o u s l y d e a l u m i n a t e d samoles w i t h o r t h o -
phosphoric a c i d i n c r e a s e s t h e s e l e c t i v i t y o t cZ-c4 o l e t i n s UP to
80%, s u p p r e s s i n g t o r m a t i o n o f o r o m o t i c s and coking. D e a c t i v a t i o n
times a r e s i g n i t i c a n t l v Prolonged (UP t o 1 0 0 h ) . A l l c a t a i y t i c
19
REF LRENCtS
1 W . W Kaedinq Und S 8 . B u t t e r . J . C o t a 1 . b l . 155(1Y80)
2 W.W.Kaeding, C.Lhu; L B.Youna. B . W e l n s t e l n , anu s . A . d u t t e r , J
Cata1.67, 159(1981)
5 L.6.Young, S . U . B u t t e r . and W.W.Kaeuing, J . ~ u t a l . / b . 41811Y8L)
4 J.C.Vedrine, A Auroux, P . D e j a i f r e , V Oucarme, H.Hoser. s Lnou.
J . C a t a l . / 3 . 14/(1982)
5 J Nunan. J C r o n i n . and J.Cunningham, J . C a t a 1 . 8 7 . I7(1984)
20
6 M . D e r e w i n s k i . J . Haber, J . P t a s z y n s k i , V . P . S h i r a l k a r , and
S . U z w i g a j . S t u d . S u r t . S c i . C a t a l . 1 8 , 209(1984)
1 J . A . L e r c h e r , ti. Rumplmayr, H . N o l l e r , A c t a Phys .Chem. 3 1 , 7 1 (1985)
8 J . A . L e r c t i e r , 6 . Rumplmavr, UPPI. C a t u l . 2 S , 215(1986)
9 A.Hahman, G.LemaY, A.Adnot, S . K a l i a s u i n e , J . C a t a 1 . 1 1 2 . 4 5 3 ( 1 9 8 8 )
10 J.H.Kim, S.Namba. l-.Yasnima, Bull.Chem.Soc.Japan 61, l O S l ( 1 9 8 8 )
11 F . L o n v l , J.Enge1hardt and D . K a l l o ; P . A . J a c o b s nnd R . A . v a n
S a n t e n ( t d i t o r s ) , Z e o l i t e s : F-acts, F i g u r e s . F u t u r e 1988 t l s e v i e r
Pub. B . V . Amsterdam. 1 3 5 /
1%S . 1 k a i , and M . Okamo t o , H .N i s h i o k a , r . Mivainoto, K . Mat s u z a k i ,
K . S u z u k i , Y.Kivazumi, T.Sano, S.Shin, A ~ p l . C a t a l . 4 9 , 143(1989)
1 5 H . V i n e k , G . Rumplmavr, ana J . A . L e r c h e r , J . C a t a l , 1 1 5 , 2 Y 1( 198Y)
14 A , J e n t y s , ci. Huiiwimavr, and J . A . L e r c h e r , A p p l . C a t o l . 5 5 , 2 9 9 ( 1 9 8 9 )
1 5 G.Ruinplmavr. ~ . A . ~ e r c n e rL,e a l i t e s , l O . 283(1990)
36 G . S e o . R.Rvoo, J . C a t a 1 . 1 2 4 , 224(1990)
1/ M . Ko j ima , F . 1.et ebvre, flnd Y . Ben Taa r it , J . Chem . Soc . Fnrad . 1 r a i l s .
86(4), /5/(1YYO)
18 G.ohlmann, H . - G . J e r s c h k e w i t z , G . L i s c h k e . B . P a r l i t z , R. t c k e l t ,
M . R i c h t e r , L . ~ . L n e n i i e28, 5 , l b l ( 1 9 8 8 )
1 9 c.D.Chans, C . T.--W.Chu, and R . F . Socha. .I . i o t a l . 8 6 . % 8 9 (1984)
20 li.ohlinann, H.-G.Jerschkewitz, G . i i s c h k e , R . k c k e l t , r . G r o s s ,
b . P a r i i t z , I . S c h u l z , K.Wehner, and D . l i m m , t h i s e d i t i o n O T
Stud.Surf.Sci.Cata1.
2 1 . I . R .Anderson. K . Fnqer, T.Mole, and R . A . R n j a d h v a k s h i , . I . C a t n l . S 8
118 (1919)
2 5 t.LotTler, Ch.Peuker. H . - G . J e r s c h k e w i t z . C a t a l . lodclv 3 .
415(1988)
24 A . -R . Grimmer and U . HaUDeIlrel S s e r , i hein. P h v s . Ler t . Y 9 . 48 / ( 19 8 S )
i 3 U . f ” l u i i e r , t .Junn, b . ~ a O w and
i ~ U.Hauoenreisser, C n e m . r h y s . L t ? t t .
lU5, 55L(1984)
Zb 1 .M.Duiican and D.C.Doualass. Chern.Phys.8/. 5 ? 9 ( 1 9 8 4 )
Z/ D . M u l l e r , 1 .Grilnze. t . H o l l a s and G.Ladwig. 7 . a n o r q . f l l l ~ . C . h e m .
500. 80(1985)
28 6 . L i t ) r o w i u s nnd W.Storek, u n p u b l i s h e d r e s u l t s .
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 21
0 1991 Elsevier Science Publishers B.V., Amsterdam
Jens Weitkamp
Institute of Chemical Technology I, University of Stuttgart, Pfaffenwaldring 55,
D-7000 Stuttgart 80 (Federal Republic of Germany)
Summary
It is likely that the catalytic performance of a much broader variety of zeolites and related
microporous materials will be routinely scrutinized in the nineties. In shape selective catalysis,
reactions of lar er molecules will play an increasing role. Even in petroleum refining and the
manufacture o f commodity petrochemicals, there is room for novel a plications of zeolite
P
catalysts. Two examples, viz. dewaxing by isomerization and isobutane butene alkylation are
discussed in some detail. The use of zeolite catalysts for the synthesis o organic intermediates
and fine chemicals continues to be a thrust area. It is desirable that synthetic organic chemists
routinely employ molecular sieve catalysts. Stereoselective catalysis in zeolites is still an
underdeveloped field. The same holds for base catalysis in zeolites, especially shape selective
base catalysis, but new approaches can be perceived in this area. Coupling of the exothermic
MTO process and the endothermic hydrocarbon cracking on ZSM-5 type catalysts allows an
almost thermoneutral production of lower olefins. The role of zeolites as hosts for a variety of
guests is recognized by an ever increasing number of researchers. Ship-in-the-bottle catalysts
or shape selective photochemistry are just a few examples for host/guest chemistry in zeolites,
the isomerization of light alkanes for octane enhancement of gasoline [5,8-101. Zeolite ZSM-S
is the prototype of shape selective catalysts. Its realm is the manufacture of commodity
petrochemicals, such as ethylbenzene or para-xylene [ 11-13]. Moreover, ZSM-5 based
catalysts are applied i n the production of gasoline from methanol [13-151, in the M-Forming
process [16,17] for octane improvement of reformer gasoline and in dewaxing of middle
distillates and lubricating oils [12,13]. For the latter process, mordenite based catalysts have
;iIso been employed [ lS,l9]. Finally, ZSM-S is used as an additive in some F C C catalysts for
octane enhancement of the gasoline produced [20,21]. The titanium containing analogue of
ZSM-5, named TS-1 [22,23], is employed for the hydroxylation of phenol to hydro-
quinone/catechol mixtures. Erionite was the catalyst in the old Selectoforming process [24,2S]
and is reported to be used again, in an improved form, i n the German Democratic Republic
for octane enhancement of reformate [26].
Until several years ago, most fundamental studies on zeolite catalysis, too, were restricted
to ;I very small number of structural types, again mostly faujasites, mordenite and ZSM-S.
Lately, this situation has changed significantly: The catalytic behavior of an ever increasing
number of alumosilicates and related microporous materials is being scrutinized, which stems,
in part, from the remarkable progress in hydrothermal synthesis and structure determination.
Likewise, the recent progress in post-synthesis modification techniques has a strong impact on
catalysis. It is another most important trend that zeolite catalysis spreads into almost all
branches of chemistry with a remarkable boom in the manufacture of organic intermediates
and fine chemicals. The present review paper is intended to describe some selected
developments in zeolite catalysis which, in the author’s opinion, deserve particular attention
in the nineties.
TABLE 1
Aluniosilicate zeolites with particular potential in catalytic research. (The dotted line
separates zeolites with 10- and 12membered*ring pores. CI denotes the Constraint Index [47],
the* data for CI were taken from [48]; CI is the Refined Constraint Index [49,50], the
CI data were taken from [51]; SI stands for the Spaciousness Index [52,53], the SI data were
taken from [53]).
Modified Constraint Index which was defined by Jacobs et al. [49,50] and the Spaciousness
Index which was introduced by Weitkamp et al. [52,53]. Wherever available, these three
indices are given for the zeolites listed in Table 1. From top to bottom, i. e., with increasing
effective pore width, both the Constraint Index and the Refined Constraint Index decrease
whereas the Spaciousness Index increases.
A number of elements other than silicon and aluminum can occur on tetrahedral sites in
the crystal lattice of microporous solids [54]. This way, a huge number of materials result, part
of which possess structures known from the alumosilicates. An example is titanium silicalite,
TS-I, with the crystal structure of ZSMd and very interesting catalytic properties in selective
oxidation reactions [22,23,55-571. Other members from this familiy of materials possess
completely new structures. This is particularly true for certain alumophosphates (AIPOds),
silicoalumophosphates (SAPOs) and the microporous solids derived from them by
24
incorporation of additional elements, such as titanium, manganese, cobalt or iron into the
lattice [58,59]. The potential of alumophosphate based molecular sieves in catalysis has
rcccntly been reviewed by Rabo et al. [60].
Within the frimily of AIP04s, very large and super-large pore molecular sieves have
recently been identified. Davis et al. recognized that V P I J is a material with unidimensional
channels formed from 18-membered rings with an approximate diameter of 1.2 nm [61-631.
The structure of VPI-5 is shown in Fig. 1 along with the related structures of A1P04-5, a
material with unidimensional 12-membered ring pores, and AIP04-l 1, a material with
unidimensional 10-membered ring pores. It is seen that the cross section of the pores in
AIP04-I 1 is strongly elliptic which renders the material particularly interesting for shape
selective catalysis. The discovery of the existence of super-large pore molecular sieves might
be a landmark in zeolite catalysis. Such materials are of great interest for the catalytic
conversion of feedstocks containing large molecules as, e. g., petroleum residues. AIPO,s,
however, possess very little o r n o acidity. As soon as silicoalumophosphates or zeolitic
:ilumosilicates with super-large pores can be synthesized this will have a tremendous impact
o n catalysis. Another material, named MCM-9 [64,65a], does contain Si-VPI-5 but it is
apparently not a pure phase. A third molecular sieve material with very large pores, i. e.,
channels formed by more than 12 tetrahedra, is AIPO4-8 [65a] the structure of which has been
determined very recently [6Sb]. A1P04-8 possesses unidimensional channels formed from
14-membered rings with the approximate dimensions 0.79 x 0.87 nm [65b].
X
- 100 I
H-Mordenite
I
(SI = 7)
1001 I
H-Beta
I
(SI = 16)
Si/Al = 6.7-
O ,,-x, -
y,*,
A y,,
--
n - 1 I
STREAM, h
conversion of ca. 70 % was achieved. The bimolecular transalkylation into naphthalene and
dimethylnaphthalenes which requires a very bulky transition state and/or intermediate, was
almost completely suppressed. With HZSM-12, H-EU-1 and H-Beta the deactivation was
moderate. Only with H-mordenite, there was a rapid deactivation due to coke formation
which has probably to do with the relatively high aluminum content rather than with the
unidimensional pore system; otherwise one would expect the same rapid deactivation for
HZSM-12 which has unidimensional pores as well.
2,6-Dimethylnaphthalene is a particularly valuable compound. It can easily be oxidized
into naphthalene-2,6-dicarboxylicacid which is a starting material for high quality polyesters,
polyamides and liquid crystals. The problem in its synthesis is that it is usually formed
together with 9 other isomers which are difficult to separate. In principle, zeolite catalysis
offers the possibility of enhanced selectivities for the 2,6-isomer, since its molecular
dimensions are smaller than those of most other isomers. Indeed, Matsuda et al. [71,72] found
that the disproportionation of 2-methylnaphthalene in H Z S M J leads to a dimethyl-
naphthalene fraction which contains the 2,6-isomer (and the 2,7-isomer which has the same
molecular dimensions) in excess of thermodynamic equilibrium. The yields, however, were
very small, presumably due to diffusional limitations. By dealumination of the external surface
with (NH&SiF6 it was shown that the shape selective disproportionation occurs inside the
ZSM-5 pores [73].
Another way to 2,6-dimethylnaphthalene is the shape selective alkylation of naphthalene
or 2-methylnaphthalene with methanol. Fraenkel et al. [74] did observe such enhanced
selectivities for 2,6- and 2,7-dimethylnaphthalene on HZSM-5, but not on H-mordenite or
HY. These authors proposed [75,76] that the shape selective conversion of naphthalene
derivatives occurs uf the cxternul surjiuce of zeolite ZSM-5, in so-called "half-cavities". This
concept which was generalized by Derouane et al. [77,78] has, however, been questioned
severely [70,79]. It is more likely that the shape selective alkylation of naphthalene or
2-methylnaphthalene on HZSM-5 occurs inside the pores and is slowed down by diffusional
limitations.
So far, most shape selectivity effects were observed in zeolite Z S M J . It is clear from the
origin of these effects [66,67] that with bulkier reactant and/or product molecules, shape
selectivity can occur in zeolites with 12-membered ring pores as well. An example is the
suppression of transalkylation of methylnaphthalenes in HZSM-12, H-EU-I, H-mordenite or
H-Beta, as shown in Fig. 2. Even in the very open and spacious pore system of zeolite Y shape
selectivity effects were observed, e. g. during the competitive hydrogenation of cyclohexene
and cyclododecene in Rh/NaY [go], hydrocracking of hydropyrenes in NiW/ultrastable Y [81]
or catalytic cracking of cis-decalin/trans-decalinmixtures in ultrastable Y [82].
Dewaxing by isomerization
The cold flow properties, e. g. the pour point and cloud point, of petroleum fractions are
largely determined by their content of normal paraffins. One method for the removal of these
disturbing waxes is shape selective hydrocracking on ZSMd based catalysts [13]. In this
process, the undesired paraffins in the boiling range of the middle distillate or lubricating oil
feedstock are converted into gasoline and C, + C4 (LPG) hydrocarbons. Another approach is
to transform the waxy paraffins into branched isomers which have considerably better cold
flow properties. This way, the yield loss necessarily associated with dewaxing by selective
hydrocracking could be avoided.
The isomerization of long chain n-alkanes can indeed be achieved on bifunctional zeolite
catalysts with a strong hydrogenation component, e. g., Pt/CaY or Pd/LaY in the presence of
hydrogen [89,90]. Under these conditions, skeletal isomerization takes place at the acid sites
via carbenium ions. These carbenium ions, however, can also undergo 0-scission, then the
overall reaction is hydrocracking. Since skeletal rearrangement and 0-scission are consecutive
reactions, the selectivity for long chain iso-paraffins is high at low conversions, but as the
conversion is increased, hydrocracking becomes more and more severe. In other words, the
yield of the desired iso-paraffins in dependence of the conversion of long chain n-paraffins
passes through a maximum. Even with the best catalysts based on zeolite Y, this maximum
yield of long chain iso-alkanes amounted to ca. 60 % (891.
Significantly higher yields of long chain iso-alkanes can be attained on certain other
zeolites, especially on bifunctional forms of Beta [91,92], ZSM-22 [43] and ZSM-23 [43]. Two
examples are shown in Fig. 3: The maximum yields of iso-decanes from n-CloHzz or iso-
tetradecanes from n-CI4H30 on Pd/H-Beta are above 70 %.
In the future, the fundamentals of dewaxing by isomerization need further clarification.
Presumably, the mechanistic reasons for the unusually high yields of iso-alkanes are different
28
for zeolite Beta on the one hand and medium pore zeolites such as ZSM-22 or ZSM-23 on the
other hand. It has been argued [43] that in the latter zeolites, B-scission is slowed down
because the highly branched precursors for the most favorable type of 13-scission (so-called
type A O-scission) cannot form due to spatial constraints. No explanation for the interesting
behavior of zeolite Beta has been proposed so far. Apparently, not all samples of zeolite Beta
do give the high yields of long chain iso-alkanes [27]. It is particularly desirable to find out the
key property of zeolite Beta which governs its catalytic performance in isomerization of
n-alkanes. Furthermore, isomerization experiments with mixtures of homologous n-alkanes
on bifunctional Beta catalysts are needed in the future.
100
-
n Decane n-Tetradecane
WIF = 570g.hImol WIF = 6LOg-hlmol
$ 60
0 Xn-De 0 Xn-Te
> Ylso
A Ycr.
0, 60
tl!
>
Ili
0
10
X
z
0
v)
OL 20
W
2
0
V
210 220 230 210 250 260 270 280 190 200 210 220 230 210 250 260 270
TEMPERATURE , ' C
Fig. 3. Isomerization and hydrocracking of long chain n-alkanes on 0.27 wt.-% Pd/H-Beta
after [92]. (The hydrogen partial pressure was 2 MPa).
Isobutane/butene alkylation
This refinery process converts the C4 by-product from catalytic crackers into high quality
gasoline. Today, alkylation is carried out either with concentrated sulfuric acid or anhydrous
hydrogen fluoride as catalysts. There is a very large incentive for replacing these processes by
a new technology which is environmentally more acceptable and safer.
In the sixties and seventies, the potential of acid faujasite catalysts in isobutane/alkene
alkylation has been explored by several groups [93-1011. Typical results are depicted in Fig. 4
and Fig. 5: 011fliefiesh zeolite, the olefin is totally converted (Fig. 4), and a perfect alkylate is
formed (Fig. 5 ) which consists fully of iso-alkanes. After a certain time on stream, however,
the olefin conversion drops and the product quality deteriorates drastically: More and more
C8-alkenes form and eventually, the zeolite no longer alkylates isobutane; rather, the butene
29
+a
- 100
0 80
I-
z
60
u)
U
W
5 40
0
0
Fig. 4. Conversion of isobutane with 1-butene (11:l) at 80 "C in the liquid phase on CeY-98
zeolite after [loo].
bp
I
W
I I I I
oligomerizes. This dramatic loss of catalyst performance is due to the build-up of low
temperature coke from the olefin. Concomitantly, the zeolite looses its hydrogen tranfer
activity.
The yields of alkylate which could be achieved on faujasite catalysts were much too low for
an industrial application. If one arbitrarily considers the product as an alkylate as long as it
contains 90 mol-% or more alkanes in the C,-fraction, then one can define an integrated yield
30
of alkylate (total mass of alkylate formed/mass of catalyst) for a given catalyst and set of
reaction conditions. Typically, these yields were in the order of SO to SO0 mg/g [loo]. Zeolite
HZSM-S was reported to be inactive in isobutane/butene alkylation a t temperatures up to
100 "C and this was attributed to the narrow pores [102]. In the meantime, a much broader
variety of zeolitic materials and techniques for their manipulation are known. Given the high
incentive for replacing the H$04 and HF catalysts we foresee a renewed interest in the use
of zeolite catalysts for isobutane/butene alkylation.
clnnamsldehyde
(CAL)
a cn = CH - C H ~ O H
Catalyst
The results summarized in Fig. 6 show that hydrogenation on platinum in Zeolite Y gave
much better selectivities for cinnamyl alcohol than on a non-zeolitic reference catalyst like
platinum on charcoal. This was interpreted by a special shape selectivity effect: Inside the
faujasite pores, the cinnamaldehyde molecule can adsorb on the platinum clusters, sitting in
the supercages, only in an end-on mode, i. e., via its carbonyl group, through the twelve-
membered ring window. By contrast, the adsorption and activation of the carbon-carbon
double bond in the center of the molecule is considered to be strongly hindered, but only as
long as the supercage is completely filled with platinum; a small cluster of six or less metal
atoms would leave enough space for cinnamaldehyde molecules to enter the supercage and
adsorb laterally, i. e., via the carbon-carbon double bond, so that hydrogenation leads to
3-phenylpropanal. This is how the authors explain that on Pt/Y with the 1 to 2 nrn clusters
the undesired hydrogenation of the carbon-carbon double bond occurs to a certain extent.
Adamantane has been found to form readily by rearrangement of tetrahydro-
dicyclopentadiene (tricycIo[5.2.1.O2b]decane, see Fig. 7) which, in turn, is easily accessible
from the Diels-Alder dimer of cyclopentadiene. Suitable catalysts for this interesting
reaction are acid or bifunctional forms of zeolite Y, such as rare earth Y (REY),
Pt-Re/REY or H Y [116,117]. For example, at temperatures around 250 "C, adamantane
selectivities between 40 and 50 % could be achieved at conversions above 50 %. Likewise,
mixtures of 1- and 2-methyladamantane were obtained on the same catalysts from tricyclo-
[6.2.1.0.2>7]undecane [ 1171. One of the conclusions from these studies was that the faujasite
structure, due to the existence of almost spherical cages, is in general a promising catalyst for
the formation of spherical molecules, and adamantane or its homologues might be just
examples for spherical molecules which can be advantageously synthesized inside the cages of
zeolites.
L
A more recent article [ 1181 reports on the formation of adamantane and its homologues
from a simple alkene, viz. 1-hexene, at 240 "C in SAPO-34, a silicoalumophosphate with the
chabazite structure. However, unlike in the above-mentioned studies with zeolite Y, the
adamantanes did not appear in the gaseous effluent from the reactor; rather, they were built
up and entrapped inside the chabazite cages (see Fig. 8), presumably again via tetra-
hydrodicyclopentadienes as intermediates. The adamantanes are, of course, too bulky to
escape through the eigth-membered ring windows of the chabazite cage. The only way to
detect them is the dissolution of the used molecular sieve, e. g., in hydrogen fluoride, followed
by extraction with an appropriate solvent, e. g., CH,Cl,. It has been again concluded from
these results [118] that the microporous catalyst with its cages of molecular dimensions can be
considered as an ideal host for transition state guests which lead to spherical, polynuclear
products. At higher reaction temperatures around 400 "C, naphthalene and its methyl
derivatives were preferentially formed inside the cages (cf. Fig. 8) of SAPO-34, probably in
related chemical pathways via dicyclopentadienes.
It is too early to judge upon the general validity of these concepts. If zeolite cages act
indeed as hosts which favor the formation of spherical products, then one could imagine a
completely new direction of zeolite catalysis: A zeolite with cages of appropriate size and
geometry could act as u templute which directs a chemical reaction towards the desired
product, which may or may not have a spherical shape. If this product is of sufficiently high
value (and/or the molecular sieve used as a reaction template sufficiently cheap) then it could
even be economical to dissolve the zeolite so that the product becomes accessible through
extraction. In the precise sense, the zeolite would then no longer play the role of a catalyst
(with a high number of closed catalytic cycles or turnovers) but simply act as a selectivity
directing reaction vessel with uppropriute moleculur dinzensions.
33
b-
Adamantane
Naphthalene
Methylnaphthalenes
Dimethylnaphthalenes
An example for such a reaction which one could envisage in a very speculative manner is
the synthesis of compounds with the dodecahedrane (C,,H,,, see Fig. 9) skeleton. Such
compounds which strongly resemble a sphere became accessible in the eighties by multi-step
syntheses, usually via precursors with the pagodane structure [ 119-1241. To our knowledge, no
systematic and professional attempt has been undertaken so far, to utilize molecular sieves for
Fig. 9. A speculative example for the use of molecular sieves as reaction templates:
Pagodanes to dodecahedranes.
dodecahedrane synthesis. The reasons are obvious: Modern synthetic organic chemistry and
professional zeolite chemistry are dealt with in different laboratories and separated from each
other. It is a managerial challenge to bring inorganic host/guest chemistry and synthetic
organic chemistry together.
34
Stereoselective catalysis
Enantioselective catalysis in zeolites is often looked upon as one of the ultimate goals. It
requires chiral centers next to the catalytically active sites. In principle, different methods can
be used to induce chiral properties.
According to Dessau [125], chiral hydrogenating catalysts result if a n acid zeolite loaded
with a hydrogenation metal, e. g., Pt/HZSM-5, is neutralized with an optically active
amine, such as S-(-)- a-methylbenzylamine (Fig. 10). O n such a catalyst, the hydrogenation of
2-Phenylbutene y 5 2-Phenylbutane
Pt/(CH 3 - C x - N H , ) Z S M - 5
I
H H
C,H,- C - CH,
I1
0
b- C,H,- k-
OH
CH,
+H2
Acetophenone 1-Phenylethanol
Afler R.M. Dessau. US Patent 4 554 262, Mobil Oil Corp.. 1985
Base catalysis
Base catalysis in zeolites is still an underdeveloped field of science and technology,
especially in comparison with acid catalysis. In the literature, essentially three approaches to
create basic sites in zeolites can be discerned. Interestingly, these attempts were almost
completely restricted to faujasites.
It was recognized early [ 1281 that faujasites exchanged with large alkali cations, especially
CsX and RbX, catalyze the side chain alkylation of toluene with methanol or formaldehyde,
rather than ring alkylation to xylenes which occurs on acid zeolites. Later, side chain
alkylation to styrene/ethylbenzene mixtures on faujasites exchanged with alkali cations has
35
been studied in detail by several groups [129-1351. It has been generally concluded that this is
a base catalyzed reaction via carbanions, although the nature of the basic sites under reaction
conditions remained a matter of debate [136,137].
Clusters from sodium metal can be generated in the pores of faujasites using various
techniques. According to Jacobs et al. [138-1411 the preferred method from the viewpoint of
catalysis is the impregnation of the dehydrated zeolite with NaN, followed by the thermal
decomposition of sodium azide under carefully controlled conditions. In faujasites modified
by this procedure, three types of sodium particles can be distinguished by ESR spectroscopy:
Na43+ clusters located inside the sodalite cages, neutral Na, clusters inside the pore system
and neutral Nay particles at the external surface. Basic framework oxygen anions next to
intracrystalline Na, clusters seem to be the active sites [141] for base catalyzed reactions such
as the isomerization of cis-2-butene [ 139,1401, the side chain alkylation in toluene,
ethylbenzene or cumene with ethene [ 1411 or regioselective ring opening in unsymmetrical
epoxides [142]. While basic zeolites prepared via the azide method appear to be very active
catalysts, it remains to be seen how stable they are against potential poisons, such as water
formed in many reactions or sulfur compounds present in traces in many feedstocks.
The third method, introduced by Hathaway and Davis [143,144], consists of impregnating
a faujasite, e. g. CsNaY, with cesium acetate followed by decomposition of the acetate at
450 "C in air or helium. It appears that the active site in such catalysts is cesium oxide rather
than metallic cesium, cesium carbonate or cesium hydroxide [ 1451. These modified faujasites
were tested in various base catalyzed reactions, such as the dehydrogenation of isopropanol to
acetone [ 144-1461 and the alkylation of methane, ethane, acetone or toluene with methanol
[146]. It will be interesting to observe whether this new method is accepted by other groups. If
Si 0,
0 0 0 0 0 0 0 0 0 0 0 0
A l PO1
Al
0 0 0 0 0 0 0 0 0 0 0 0
Zeolite H'B He H@
IAcid 1
o \ i / V S /o\;
i /VSi /o\si /O\$/O
/ \ / \ I \ / \ / \ / \
0 0 0 0 0 0 0 0 0 0 0 0
OH8 OH8 OH 0
Sip0 ? 0
(Base 1
/ \
i ' o i ' o o/\o d'o o/\o 0 0
so, this could foster base catalysis in zeolites including, perhaps, shape selective base catalysis
with its huge potential in the manufacture of organic intermediates and fine chemicals.
A hypothetical approach towards a new generation of molecular sieve Briinsted bases
might be seen in the preparation of microporous silicophosphates, either by direct synthesis or
post-synthesis modification. As shown schematically in Fig. 11, and for obvious reasons, a
molecular sieve S i 0 2 , such as silicalite 1 or 2, has no lattice charge. The same is true for the
overuff lattice in AIP04s due to the strictly alternating arrangement of @lo4)- and (PO4)+
tetrahedra. Alumosilicate zeolites are cation exchangers and, in their H + forms, strong
Briinsted acids. By mere analogy and in a formal manner a porous silicophosphate would be
expected to be an anion exchanger and, in its OH- form, a Briinsted base.
In a triangular compositional diagram (Fig. 12), the alumosilicate zeolites and the
hypothetical silicophosphates are just limiting cases which are represented by positions on the
Si02-A102' and SO2-PO2+ connecting lines, respectively. There exist a whole field of cation
exchangers, embracing both the SAPOs and alumosilicate zeolites, and a whole field of
A Electroneutrality
Field of anion
/e xc ha ng e rs ?
.....................
-
Field of cation :. Al- high :
exchangers : rich silica :
).
ZEOLITES
Fig. 12. Schematic representation of the possible compositions of molecular sieve materials in
the Si02/A102/P02 system, adapted from Flanigen et al. [%I.
37
hypothetical anion exchangers, and these two fields are separated from each other by the
electroneutrality line which connects the AIPO4s and SiO2.
It has, in fact, been reported [147] that the overall framework charge in a zeolite can be
changed from negative to positive if a synthetic zeolite is treated with a melt of ammonium
dihydrogen phosphate at 230 "C. For the resulting materials with anion exchanger properties
the name phosphated aluminosilicates or PASOs [147] was coined. It remains to be seen
whether the new procedure is reliably applicable to other zeolites and by other groups. If so,
the door to a new class of microporous Bronsted bases would be open.
It is sometimes difficult to distinguish unambiguously between acid and base catalysis
on molecular sieve materials. Recently, Dessau [ 148,1491 proposed the conversion of
HZSM-5
(SIIAI = 35)
HC CH
T = 225OC I X=25%
CHS-C-CH,-CH,-C-CH, 2,5-Dlmethyl-
I1 I1 luran
0 0
Acetonylacetone
-C /C%
-.,A- H,C
I
H,C, /CH
II X=51%
S=95%
NaZSM-5
$
(SI/Al = 13 000) 0
(Na/AI = 300) 3-Methylcyclo-
T = 300% pentenone
Fig. 13. Conversion of acetonylacetone as a valuable test reaction for distinguishing between
acid and base catalysis in zeolites after [149].
2,5-hexanedione (acetonylacetone) as a test reaction which, from the products formed, allows
a safe discrimination (Fig. 13). On acid zeolites, e. g. HZSM-5, 2,s-dimethylfuran is formed
almost exclusively at medium conversions; base catalysis, on the other hand leads to 3-methyl-
cyclopentenone, again in a very high selectivity a t conversions above 50 %. A broader
application of this test reaction could be very helpful in future research on base catalysis in
zeolites.
zeolite catalysts. Zeolite host/guest chemistry which is, at this time still at its infancy, can be
expected to become a thrust area in the nineties. In a few review articles [113,153,154], the
potential of zeolite host/guest chemistry for catalysis has been outlined and the different
approaches were described.
In complete analogy with a ship-in-the-bottle, transition metal complexes which are too
bulky to escape through the twelve-membered ring window of faujasite, can be synthesized in
its supercages from sufficiently small building blocks which do have access to the cages.
The best known examples are phthalocyanine complexes of cobalt, nickel, copper and iron
[ 155-1591. For their preparation, the transition metal ion is first exchanged into the zeolite
whereupon the complex is synthesized by reaction with 1,2-dicyanobenzene at temperatures
around 300 "C. Usually, part of the phthalocyanine complexes are formed at the external
surface, but this part can be selectively removed by Soxhlet extraction. Iron phthalocyanine in
NaY has also been synthesized from [HFe3(CO),,]- which was first oxidized and then reduced
under controlled conditions whereupon 12-dicyanobenzene was admitted [ 1601. Metal
phthalocyanines immobilized in zeolite Y have been described to exhibit interesting catalytic
properties, e. g., in oxidation reactions with iodosobenzene [ 158,1591: Reactant shape
selectivity occurred with cyclohexane/cyclododecane mixtures, n-octane was oxidized in a
regioselective manner and stereoselective oxidation of methylcyclohexane and norbornane
took place. Recently, an electron donor/acceptor complex (Na+)4 (FePc)@/NaY was
prepared from iron phthalocyanine (FePc) encapsulated in NaY by reaction with sodium
naphthalene, Na+ (CloH8)-, and this complex gave unusually high ratios of trans-2-butene/
cis-2-butene in the selective hydrogenation of butadiene [ 1601.
Another guest which has been synthesized in zeolite Y as a host is cobalt salen [161].
About one Co2+ per two supercages was exchanged into NaY followed by sublimation of the
free ligand salen [1,6-bis(2-hydroxyphenyl)-2,5-diaza-l,5-hexadiene]into the zeolite voids.
Cobalt salen, a tetradentate chelate has dimensions greater than the window diameter of
zeolite Y, hence it is a true ship-in-the bottle. The complex and its pyridine adduct were found
to form adducts with dioxygen and can be considered as hemoglobin mimic [161].
Metal clusters entrapped in the intracrystalline voids are of utmost importance in zeolite
catalysis. Since the pioneering work of Gallezot et al. [162,163] it is known that the size and
location of such clusters depend, to a large extent, on the preparation conditions. The metal
can be introduced by ion exchange with its cation or a cationic complex, especially an ammine
complex, followed by a controlled thermal treatment including reduction. Metals which are
difficult to introduce by ion exchange in aqueous suspension, such as molybdenum, vanadium
and others, can often be easily incorporated by solid state ion exchange which has recently
found much interest [ 164-1661. An alternative method for preparing highly dispersed metal
clusters in molecular sieves is the adsorption and controlled decomposition of volatile metal
compounds, mostly carbonyls [167]. In all these methods, metal atoms or small metal
oligomers are probably formed as intermediates which migrate rapidly through the zeolite
pores and coalesce to form larger agglomerates. Once these particles are larger than the
windows of the cages the metal agglomerates find themselves entrapped, e. g., in a supercage
40
of faujasite. In other words, it is the ship-in-the-bottle principle which enables the preparation
of highly dispersed metals in zeolites.
Similarly, the encapsulation af metal carbonyls in zeolites has found considerable interest
because many carbonyls can act as selective catalysts. An example is the ship-in-the-bottle
formation of Pd,,(CO), clusters in NaY [168].
While, in the eighties, the potential role of zeolites as hosts for a variety of guests has
clearly been recognized, host/guest chemistry has been essentially confined to faujasites. It is
likely that, in the nineties, host/guest chemistry will be systematically extended to additional
microporous materials, such as AlPO,-8, VPI-5 or the hexagonal counterpart of faujasite,
Breck's Structure Six,which can now be synthesized in a pure form using a crown-ether based
supramolecule, viz. 18-crown-6,as template [ 1691.
it;
Norrish Type II Reaction: C6H5
C6H5
R H H
L
~~~~~ ~ ~~~~
Fig. 15. Shape selective photolysis of alkanophenone guests in zeolites as hosts after [170].
this was attributed to the restriction of the rotational motion of the central u bond in the
1,4-biradical. In other words and in the language of the zeolite community, this is a
photochemical example for restricted transition state shape selectivity [66,67]. Interestingly,
zeolite Beta with its intermediate pore width clearly favors cyclization, especially for
octadecanophenone with its long alkyl chain, which is not yet understood.
Similar photochemical studies with molecules adsorbed in zeolites were carried out by
Turro et al. [171,172] and Zimmermann and Zuraw [173]. It has been found, for example,
that the photochlorination of n-alkanes in pentad zeolites proceeds with a high selectivity for
monochlorination at terminal methyl groups [172].
Acknowledgements
The author expresses his gratitude to the following funding institutions which have
sponsored his research on catalysis in zeolites: Deutsche Forschungsgemeinschaft,
Bundesministerium fur Forschung und Technologie, Fonds der Chemischen Industrie and
Max Buchner-Forschungsstiftung.
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Future; Proc. 29th IUPAC Congress, Cologne, June 5-10, 1983, Pergamon Press,
Oxford, 1984, pp. 327-336.
G. S. Lee, J. J. Maj, S . C. Rocke and J. M. GarcCs, Catal. Letters 2 (1989) 243-248.
J. Weitkamp and M. Neuber, in: Proc. Intern. Symposium on Chemistry of
Microporous Crystals, Tokyo, Japan, June 26-29, 1990, accepted for publication.
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M. F. M. Post (Eds.), Zeolites for the Nineties; Recent Research Reports,
8th Intern. Zeolite Conference, Amsterdam, July 10-14, 1989, pp. 431-432.
T. Matsuda, K. Yogo, T. Nagaura and E. Kikuchi, J. Japan Petrol. Institute 33 (1990)
214-220.
T. Matsuda, K. Yogo, Y. Mogi and E. Kikuchi, Chemistry Letters (1990) 1085-1088.
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Amsterdam, July 10-14, 1989, pp. 425-426.
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1412-1413.
H.W. Haynes, Jr., J.F. Parcher and N.E. Helmer, Ind. Eng. Chem. Process
Des. Dev. 22 (1983) 401-409.
H.B. Mostad, T.U. Riis and O.H. Ellestad, Appl. Catal. 58 (1990) 105-117.
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T. Yamaguchi and T. Tanaka (Eds.), Acid-Base Catalysis, Kondansha/VCH-Verlags-
gesellschaft, Tokyo/Weinheim, 1989, pp.313-3 18.
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Catalysis, Sihfok, Hungary, May 13-16, 1985, pp. 261-270.
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(Eds.), Catalysis- Concepts and Applications; Proc. 9th National Symposium on
Catalysis, Madras, India, Dec. 15-17, 1988, pp. OR 11-1 to OR 11-11.
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Kh.M. Minachev, E.S. Mortikov, S.M. Zen’kovskii, N.V. Mostovoi and N.F. Kononov,
Preprints, Div. Petr. Chem., Am. Chem. Soc. 22 (1977) 1020-1024.
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Science and Catalysis, Vol. 5, Elsevier, Amsterdam, Oxford, New York, 1980,
pp. 65-75.
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London, Philadelphia, Rheine, 1980, pp. 858-865.
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. I
R.F. P art on, D.R.C. Huybrechts, Ph. Buskens and P.A. Jacobs
K.U. Leuven, Dept. B i o t e c h n i s c h e Wetenschappen, Laborat orium voor
Oppervlaktechemie, K a r d i n a a l M e r c i e r l a a n 92, 8-3030 Heverlee (Leuven),
Belgium
SUMMARY
The o x i d a t i o n o f u n a c t i v a t e d alkanes was s t u d i e d on z e o l i t e encaged
p h t h a l l o c y a n i n e s w i t h t e r t i a r y b u t y l hydroperoxide and on t i t a n i u m
s i l i c a l i t e w i t h aqueous hydrogen p e r o x i d e as o x i d a n t . On b o t h t y p e s o f
c a t a l y s t s secondary and/or t e r t i a r y a l c o h o l s and ketones a r e formed. The
o x y f u n c t i o n a l i z a t i o n occurs i n a r e g i o s e l e c t i v e way on t h e o u t e r carbon
atoms o f t h e hydrocarbon c h a i n , t h u s r e f l e c t i n g t h e shape s e l e c t i v e
properties o f the catalysts.
INTRODUCTION
The ma jo r industrial applications of zeolites in refinery and
pet roc hemic a l o p e r a t i o n s a r e r e l a t e d t o r e a c t i o n s where t h e z e o l i t e i s used
as an acid or bifunctional catalyst, e.g. cracking, hydrocracking,
isomerization, alkylation, etc. [l].
Th eref ore, up t o now most o f t h e
fundamental work i n t h e f i e l d o f z e o l i t e s has been c o n c e n t r a t e d on t h e i r
a c i d o r metal s t a b i l i z i n g p r o p e r t i e s . On t h e c o n t r a r y , relatively l i t t l e
e f f o r t s have been done t o e x p l o i t t h e u n i q ue f e a t u r e s o f z e o l i t e c a t a l y s t s ,
such as shape s e l e c t i v i t y , i n o t h e r t y p e s o f r e a c t i o n s [ 3-51. One o f t h e
l e a s t studied z e o l i t e catalyzed reactions i s t h e o x y f u n c t i o n a l i z a t i o n o f
alkanes i n t h e l i q u i d phase. N e v e r t h e l e s s , t h e g r e a t abundance o f alkanes
makes them t o one o f t h e g r e a t e s t r e s o u rces f o r t h e energy and f o r t h e
chemical industry. The extreme low r e a c t i v i t y o f alkanes makes their
a c t i v a t i o n and f u n c t i o n a l i z a t i o n a c h a l l e n g e f o r many chemical s c i e n t i s t s .
D u r i n g t h e l a s t 10 y e a r s many e f f o r t s have been done i n t h i s area u s i n g
homogeneous c a t a l y s t s [ Z ] . Therefore, m a j or c o n t r i b u t i o n s o f r e s e a r c h e r s i n
the f i e l d o f z e o l i t e catalyzed reactions f o r t h e f u n c t i o n a l i z a t i o n of
alkanes cannot h o l d o f f . I n t h i s work a l k a nes a r e o x i d i z e d by a p e r o x i d i c
oxygen source (ROOH) to the c o r r e s p o n ding alcohols and ketones with
maintenance o f t h e carbon c h a i n s t r u c t u r e , according t o t h e f o l l o w i n g
genera l r e a c t i o n scheme:
ExDerimental
Materials
A sample o f NaY w i t h a Si/A1 r a t i o o f 2.46 was purchased f r o m Ventron.
VPI-5 was s y n t h e s i z e d a c c o r d i n g t o a r e c e n t l i t e r a t u r e procedure [14]. 1,2-
Dicyanobenzene (DCB) (+98%), f e r r o c e n e (FeCp2) (+98%), t e r t i a i r y butyl
hy dro pero x ide (t.BHP) (70% i n w a t e r ) , acetone, dichloromet hane (CH2C12), n -
hexane, n-heptane, n-octane, n-nonane and n-decane (all +99%) were
purchased f rom A l d r i c h . H e - p h t h a l l o c y a n i n e (H2Pc) (+98%) was purchased f rom
A l d r i c h and F e - p h t h a l l o c y a n i n e (FePc) (+98%) f r o m Strem Chemicals.
F erric enium - Y i s p r e p a r e d by adding 5 g o f a i r - d r y NaY t o 50 m l o f a
s o l u t i o n o f f e r r o c e n e i n acetone c o n t a i n i n g 84 mg (=1 complex p e r u n i t
c e l l ) o f FeCp2, f o l l o w e d b y a i r d r y i n g a t 343 K. The l a t t e r s o l i d i s mixed
w i t h 5 g o f DCB and h e a t e d under He atmosphere a t 423 K f o r 4 hours. T h i s
khaki -coloured sol i d is succesively soxhlet extracted with acetone,
p y r i d i n e and a g a i n w i t h acetone, u n t i l a c o l o u r l e s s e x t r a c t i s obt ained.
The f i n a l c a t a l y s t i s a i r d r i e d a t 343 K. FePcVPI-5 i s s y n t h e s i z e d a t 523
i n s t e a d o f 423 K a c c o r d i n g t o t h e same procedure.
49
Characteri sat i o n
I.R. c h a r a c t e r i s a t i o n o f t h e samples i s c a r r i e d o u t u s i n g t h e K6r
t ec hnique. U.V. spectroscopy was used for the semi-quantitative
d e t e r m i n a t i o n o f t h e amount o f i n t r a c r y s t a l l i n e p h t h a l l o c y a n i n e s , after
d i s s o l u t i o n o f t h e z e o l i t e i n c o n c e n t r a t e d s u l f u r i c a c i d (0.1 g o f c a t a l y s t
i n 10 m l o f c on c e n t r a t e d H2S04 f o r 4 h ) . The i r o n c o n t e n t o f t h e samples i s
determined by chemical a n a l y s i s . X - r a y powder d i f f r a c t i o n i s used t o ensure
good c r y s t a l l i n i t y o f t h e z e o l i t e a f t e r t h e s y n t h e s i s and p u r i f i c a t i o n
procedures.
R eac t io n Drocedure
O x y f u n c t i o n a l i z a t i o n r e a c t i o n s o f n - a lkanes a r e c a r r i e d o u t a t room
temperature and atmospheric p r e s s u r e w i t h t.BHP as oxidans and acetone as
s o l v e n t . Product a n a l y s i s was done w i t h GC on a 50 m CP S i l - 8 6 c a p i l l a r y
column f rom Chrompack.
R e s u l t s and d i s c u s s i o n
C h a r a c t e r i s a t i o n o f encaqed FePc
I n spite o f d i f f e r e n t conditions, such as t h e r e s p e c t i v e s y n t h e s i s
c o n d i t i o n s mentioned above, a r e a p p l i e d f o r FePc and FeCp2 impregnat ion on
NaY and VPI-5 is the application o f the st andard s o x h l e t extraction
procedure s t i l l s u f f i c i e n t t o remove a l l i r o n f rom t h e s o l i d s . When i n s i t u
synthesis of FePc is made in both molecular sieve structures, the
e x t r a c t i o n procedure removes o n l y p a r t o f t h e i r o n . Thus a l l r e s i d u a l i r o n
p r e s e n t i s ' a s s o c i a t e d w i t h encaged FePc. Indeed, after extraction the
c h a r a c t e r i s t i c l i n e s o f Cp2 (814 c m - l ) and DC6 (965 c m - l ) a r e absent as
shown by I . R . d a t a [ 1 5 ] .
Chemical a n a l y s i s combined w i t h U.V. spectroscopy o f samples d i s s o l v e d
i n c onc ent rat e d s u l f u r i c a c i d a l l o w t o d et ermine t h e amount o f FePc and
H2Pc pre s ent i n t h e molecular sieves. The NaY samples used f o r the
c a t a l y t i c experiments have about 1 FePc f o r e v e r y 77 supercages. I n case o f
VPI-5 samples t h e amount o f i n t r a c r y s t a l l i n e FePc corresponds t o 0.021 f o r
each u n i t c e l l .
M o l e c u l a r g r a p h i c s a n a l y s i s o f FePc l o c a t e d i n t h e supercages o f NaY
z e o l i t e s shows a s a d d l e - t y p e d e f o r m a t i o n o f t h e p l a n a r FePc molecule which
det e rmines t h e f r e e a p e r t u r e s t o t h e a c t i v e s i t e [15]. I t c o n t r a s t s w i t h
FePc encaged i n VPI-5 where no d e f o r m a t i o n o f t h e c h e l a t e occurs.
C a t a l y t i c a c t i v i t v w i t h FePcY
Zeolite-enclosed FePc are suitable catalysts for the selective
o x i d a t i o n o f p a r a f f i n e s t o ketones and a l c o h o l s a t ambient t emperat ure and
pre s s ure w i t h t.BHP as oxygen atom donor. O x i d a t i o n r e a c t i o n s a r e performed
50
r e s p e c t i v e l y . The m a j o r s i d e r e a c t i o n i s t h e decomposition o f t h e o r g a n i c
peroxide t o molecul a r oxygen and t. b u t a n o l .
F i g . 1 a l s o shows a f a s t e r d e a c t i v a t i o n r e a c t i o n f o r an alkane when
t h e c h a i n l e n g t h i n c r e a s e s f r o m 6 t o 10 carbon atoms. The reason f o r t h i s
behav iour i s n o t c l e a r .
15
5, .~
h
FePcY
v
3 0 octane
10 FePcY
C
0
.I u decane
rA
h FePcY
w
b ~ 1 0 0 % ketone
C formation
0 5
u octane
FePcVPI- 5
0
0.0 0.5 1 .o 1.5
Ratio of t.BHP
to alkane (mol/mol)
A
ketone alcohol C2lC3 C2IC4
100, I
Catalyst Catalyst
TABLE 1
R e g i o s e l e c t i v i t y i n t h e ketone f r a c t i o n f o r t h e o x i d a t i o n o f C6 t o C10 n -
a1 kanes on FePcY c a t a l y s t a expressed as s t a n d a r i z e d molar r a t i o s b o f C2/C3
and C2/ (C4tC5) .
Substrate Regi osel e c t i v i t y C
Ketone f r a c t i o n
C2/C3 C2/(C4tC5)
n - hexane 0.92
n - heptane 1.15 1.51
n -o c t a ne 1.29 1.95
n-nonane 1.38 2.80
n-decane 1.56 2.59
Conclusions
I r o n - p h t h a l l o c y a n i n e s a r e encaged i n m o l e c u l a r s i e v e s by an i n s i t u
s y n t h e s i s f rom ferrocenium-Y and f e r r i c e n i u m-VPI -5. The a c t i v i t y o f i r o n -
p h t h a l l o c y a n i n e s i n z e o l i t e Y i s h i g h e r t h a n i n t h e VPI-5 c a t a l y s t which i n
t u r n exceeds t h o s e o f t h e f r e e complexes as shown by t u r n o v e r numbers o f
respectively, 6,000, 2,000 and 25. However, iron-phthallocyanine-VPI-5 i s
more s t a b l e t h a n t h e i r o n - p h t h a l l o c y a n i n e - Y c a t a l y s t , which t u r n s i n a c t i v e
a f t e r t u r n o v e r numbers h i g h e r t h a n 6,000, and t h e f r e e complex s u f f e r s f rom
v e r y f a s t o x i d a t i v e d e s t r u c t i o n . Shape s e l e c t i v i t y i n t h e r e g i o s e l e c t i v e
o x i d a t i o n o f alkanes i s h i g h e r on FePcY t h a n on FePcVPI-5, which i n t u r n i s
higher t h an on the non-selective homogeneous catalyst. This can be
explained by a combined e f f e c t of steric constraint imposed by the
framework of the molecular sieve and the deformation of the
phthallocyanine. The shape s e l e c t i v e o x i d a t i o n o f t h e secondary carbon
atoms o f normal alkanes i n c r e a s e s w i t h t h e c h a i n l e n g t h .
54
ExDerimental
TS-1 was p r e p a r e d by t h e h y d r o t h e r m a l procedure d e s c r i b e d i n example 2
o f US 4,410,501. I t s i n f r a r e d spectrum i s c h a r a c t e r i z e d by an I R band a t
960 cm-l, as r e p o r t e d f o r T S - 1 [20-211, and no e x t r a z e o l i t i c c r y s t a l l i n e o r
amorphous phases c o u l d be d e t e c t e d by XRD o r SEM.
The o x i d a t i o n r e a c t i o n s were conducted a t 373K under v i g o r o u s s t i r r i n g
i n a s t a i n l e s s s t e e l b a t c h r e a c t o r p r e v i o u s l y f l u s h e d w i t h N2. A f t e r
c o m p l e t i o n o f t h e r e a c t i o n , t h e two l i q u i d phases (H202 and alkane) were
homogenized w i t h an excess o f acetone. The o x i d a t i o n p r o d u c t s were analyzed
by GC on a 50 m CP S i l - 8 8 c a p i l l a r y column f rom Chrompack, u s i n g t o l u e n e as
internal s t a nd a r d . W i t h i n t h e accuracy o f t h e GC a n a l y s i s , yields of
a l c o h o l s and ketones add up t o 100% on a carbon b a s i s . H202 conversions
were det e rmined by c e r i m e t r i c t i t r a t i o n [33].
R e s u l t s and d i s c u s s i o n
F i g . 3 shows t h e o x i d a t i o n p r o d u c t s o b t a i n e d i n t h e o x i d a t i o n o f n -
hexane w i t h 35% aqueous H202 as a f u n c t i o n o f r e a c t i o n t i m e .
The o x i d a t i o n p r o d u c t s a r e d e r i v e d f r o m n-hexane by o x i d a t i o n a t t h e
secondary carbon p o s i t i o n s , w h i l e o x i d a t i o n o f p r i m a r y C - H bonds i s below
d e t e c t i o n 1 i m i t s . Wi t h i n c r e a s i n g n-hexane conversion, t h e s e l e c t i v i t y f o r
ketones i n c r e a s e s a t t h e expense o f t h a t f o r a l c o h o l s , i n d i c a t i n g t h a t t h e
o x i d a t i o n oc c u r s i n two c o n s e c u t i v e s t e p s, i.e. hexane i s o x i d i z e d t o a
m i x t u r e o f 2- and 3-hexanols, w h i c h i s t h e n f u r t h e r o x i d i z e d t o 2- and 3 -
hexanones. The absence o f i s o m e r i s a t i o n o f t h e p r o d u c t s was c o n f i r m e d by
t h e f o r m a t i o n o f o n l y 2-hexanone o r 3-hexanone when r e s p e c t i v e l y 2-hexanol
o r 3-hexanol were used as s u b s t r a t e s . Theref ore, t h e o v e r a l l r e a c t i o n
scheme f o r n-hexane o x i d a t i o n on TS-1 can be r e p r e s e n t e d as f o l l o w s :
55
H202
2-hexanol 1 2-hexanone
H202
n-hexane , H202
3-hexanol 1 3-hexanone
I r I
3-hexanone
/
/
/ lZ@#2-hexanone
EB 2-hexanol
total
-
n
0 0.5 1 2 3
TABLE 2
Alkane o x i d a t i o n s by H202 on TS - l a
F o r t h e d i f f e r e n t n - a l k a n e s as w e l l as o f t h e f o u r hexane isomers t h e
e f f i c i e n c y o f H202 use f o r o x i d a t i o n i s h i g h on TS-1, b u t decreases as t h e
dimensions of the substrate increase. The t o t a l amount of oxygenated
p r o d u c t s i s almost statistically d i s t r i b u t e d over t h e d i f f e r e n t carbon
p o s i t i o n s , w i t h o n l y a s l i g h t s e l e c t i v i t y f o r o x i d a t i o n a t t h e w-1 p o s i t i o n
o f t h e carbon c h a i n . W i t h i n t h e ketone f r a c t i o n however, a v e r y pronounced
s e l e c t i v i t y f o r 2-ketones i s observed. T h i s means t h a t t h e f i r s t o x i d a t i o n
step, i.e. the formation o f alcohols, i s only l i t t l e regioselective,
whereas i n t h e second o x i d a t i o n s t e p , t h e 2 - i s o m e r s o f t h e a l c o h o l m i x t u r e
a r e s e l e c t i v e l y f u r t h e r o x i d i z e d t o 2 - k e t o n e s . T h i s s e l e c t i v i t y i s imposed
by t h e shape s e l e c t i v e p r o p e r t i e s o f TS-1. Furthermore, i t i s seen t h a t f o r
branched a1 kanes, tertiary C-H bonds are selectively oxidized over
secondary ones. The a l k a n e o x i d a t i o n on TS-1 t h u s f o l l o w s t h e ' n o r m a l '
r e a c t i v i t y o r d e r : t e r t i a r y C-H > secondary C-H >>> p r i m a r y C-H.
Furthermore the H202 yield decrease with increasing substrate
dimensions. T h i s o f f e r s s t r o n g e v i d e n c e f o r an i n t r a c r y s t a l l i n e r e a c t i o n .
Indeed, because o f t h e g e o m e t r i c a l c o n s t r a i n t s imposed by t h e p o r e geometry
of TS-1 on the catalyzed reactions, the oxidation rate of organic
s u b s t r a t e s decreases as t h e i r dimensions i n c r e a s e , and t h e r e f o r e t h e main
side reaction, i.e. t h e r m a l and c a t a l y t i c d e c o m p o s i t i o n o f H202 t o 02,
becomes more c o m p e t i t i v e .
F i g . 4 shows t h e dependance o f t h e TS-1 c a t a l y z e d n-hexane o x i d a t i o n
on t h e amount o f s o l v e n t i n t h e r e a c t i o n m i x t u r e .
100
3-hexanone
80
be
W
@%%l
2-hexanone
3-hexanol
.-
v1
60
h 2-bexanol
2 40
C 0 total
0
20
0
0 10 20 30 45 60 90
Acetone (ml)
F i g . 4 . n-Hexane o x i d a t i o n by H202 on TS-1 as a f u n c t i o n o f acetone
c o n c e n t r a t i o n . R e a c t i o n c o n d i t i o n s : 500 mg o f TS-1, 115 mmoles o f n-hexane,
240 mmoles o f H202 (35% i n H20), I h r a t 373K and 700 RPM.
80 0
m
h
ae
W d
0
60 0
C 0,' U
0
.I
vl .' 0 O
2-bexanol
L, 40
a2
P
El
$ 20 0
0 ++1
0 . 2 5 . 5 0 .75 1.00 0 . 2 5 . 5 0 .75 1.00
TS-1 (g)
As i s seen i n F i g . 4 , t h e acetone c o n c e n t r a t i o n a l s o s t r o n g l y a f f e c t s
the k et o ne/ a lc o h o l ratio of the oxidation product s. The decreasing
s e l e c t i v i t y f o r ketones w i t h i n c r e a s i n g acetone c o n c e n t r a t i o n i s p r o b a b l y
p a r t l y connected w i t h t h e v a r i a t i o n o f t h e conversion, b u t i s a l s o caused
by t h e v a r i a t i o n o f hexane c o n c e n t r a t i o n i n t h e aqueous H202 phase. Indeed,
58
0
II
Ti
H202 OH
\ /
Ti
OOH
- 0-0
\
Ti
< + H20
Scheme 1: F o r m a t i o n o f s u r f a c e peroxo s p e c i e s by r e a c t i o n o f T i - s i l i c a l i t e
w i t h H202.
C o n s i d e r i n g t h e i n e r t n e s s o f s a t u r a t e d hydrocarbons, t h e i r oxidation
p r o b a b l y r e q u i r e s a h o m o l y t i c mechanism, involving radical intermediates.
Furthermore, i t was shown above t h a t t h e p r i m a r y o x i d a t i o n p r o d u c t s a r e
alcohols, ketones b e i n g formed i n a c o n s e c u t i v e o x i d a t i o n . A tentative
mechanism f o r a l k a n e h y d r o x y l a t i o n on TS-1 i s r e p r e s e n t e d i n Scheme 2, in
analogy with the mechanism proposed for the stoichiometric alkane
o x i d a t i o n s by V-peroxocomplexes [ 3 1 ] .
-0
\ /
Ti
d
-0*
\
Ti
H-C-
-
/
\
\
0-0-H
Ti
* /
C-
\
- 0
II
Ti
HO-C-
/
\
Conclusions
T i t a n i u m s i l i c a l i t e can be used as a selective catalyst for the
o x i d a t i o n o f u n a c t i v a t e d a1 kanes by aqueous hydrogen p e r o x i d e . Secondary
and/or t e r t i a r y a l c o h o l s a r e t h e p r i m a r y o x i d a t i o n product s, t h e f ormer
ones a r e f u r t h e r o x i d i z e d t o ketones i n a c o n s e c u t i v e r e a c t i o n . The shape
s e l e c t i v i t e p r o p e r t i e s o f t h e c a t a l y s t favour a r e g i o s e l e c t i v e o x i d a t i o n a t
t h e 0-1 p o s i t i o n o f t h e carbon c h a i n which i s most pronounced i n t h e
f o r m a t i o n o f ketones. A d d i t i o n o f a p o l a r s o l v e n t t o t h e r e a c t i o n system
improves t h e mutual s o l u b i l i t y o f t h e aqueous H202 phase and t h e alkane
phase, and r e s u l t s i n an i n c r e a s e o f t h e r e a c t i o n r a t e and a decrease o f
t h e k et o ne/ a lc o h o l r a t i o o f t h e p r o d u c t s. A homolyt ic, non-free r a d i c a l
c h a i n r e a c t i o n mechanism, i n v o l v i n g T i peroxo compounds i s proposed.
GENERAL CONCLUSIONS
ACKNOWLEDGMENTS
RFP and DRCH acknowledge a f e l l o w s h i p f rom t h e B e l g i a n Fund o f
S c i e n t i f i c Research.
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60
4. H. van Bekkum and H.W. Kouwenhoven, Recl. Trav. Chim. Pays-Bas, 108
(1989) 283-294.
5. W.F. H o l d e r i c h , Stud. S u r f . S c i . , 49 (1989) 69-93.
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7. D. Mansuy, Pure Appl. Chem., 59 (1987) 759-770.
8. I . Tabushi, Coord. Chem. Rev., 86 (1988) 1-42.
9. N. Herron, G.D. Stucky and C.A. Tolman, J. Chem. SOC. Chem. Commun.,
(1986) 1521- 1522.
10. G. Meyer, D. Wohrle, M. Mohl and G. S c h u l z - E k l o f f , Z e o l i t e s , 4 (1984)
30-34.
11. B.V. Romanovsky, Proceed. 8 t h I n t . Congr. C a t a l ., V e r l a g Chemie,
Weinheim, 4 (1984) 657-667.
12. N. Herron, J. Coord. Chem., 19 (1988) 25-38.
13. T. Kimura, A. Fukuoka and M . I c h i k a w a , Shokubai, 30 (1988) 444-447.
14. P.J. Grobet, J.A. Martens, I . B a l akrishnan, M. Mertens and P.A.
Jacobs, Appl. C a t a l . , 56 (1989) L21-L27.
15. R.F. Parton, L. U y t t e r h o e v e n and P.A. Jacobs, Second I n t . Symp.
Heterog. C a t a l . & F i n e Chemicals, P o i t i e r s , (1990).
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17. Cytochrome P-450: S t r u c t u r e , Mechanism and B i o c h e m i s t r y , Ed. P.R.
O r t i z de M o n t e l l a n o , Plenum Press: New York, (1986).
18. J. Haber, R. Iwanejko and T. Mlodnicka, J . Molec. C a t a l . , 55 (1989)
268- 275.
19. R.A. L e i s i n g , R.E. Norman and L. Que, Jr., I n o r g . Chem., 29 (1990)
2555-2557.
20. M. Taramasso, G. Perego and B. N o t a r i , U.S. Pat . 4,410,501 (1983).
21. G. Perego, G. B e l u s s i , C . Corno, M. Taramasso, F. Buonomo and A.
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(1986) 129-136.
22. B. N o t a r i , Stud. S u r f . S c i . C a t a l . , 37 (1987) 413-425.
23. U. Romano, A. E s p o s i t o , F . Maspero, C . N e r i and M.G. C l e r i c i , Stud.
S u r f . S c i . C a t a l . ,55 (1990) 33-41.
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240-242.
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G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeotes 61
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
The sorption of methane, nitrogen and carbon dioxide and their binary
mixtures has been studied i n both silicalite-1 and Na-Y zeolites. The above
sorbates have increasing polarity and the effect of change of polarity on
their sorption behaviour in the uncharged silicalite and highly charged Na-Y
frameworks has been determined. Separation factors calculated from the
initial slopes of the single component isotherms are compared with those
obtained by experiment for both sorbents. Three isotherm models have
been tested for their ability to predict the sorption of nitrogedmethane
mixtures in Na-Y.
1NTRODUCTION
The separation of gas mixtures by pressure swing adsorption (PSA) is
becoming more widely used as the cost of energy increases. The design and
optimisation of PSA separation units requires a detailed knowledge of
equilibrium adsorbate mixture data over the temperature and pressure
range likely to be used in such units. There is also a need to select the
adsorbent with the optimum properties for the specific adsorbate mixtures
to be separated. This paper describes some interesting results which
compare the sorptions of binary mixtures of CH4, N2 and COz in two zeolites
with completely different surfaces. The first is silicalite-1, which is the pure
s’ilica end member of the zeolite ZSM-5, and Na-Y a more open, highly
charged zeolite containing a high concentration of aluminium atoms in the
framework and sodium ions to neutralize the negative charge introduced in
the framework by the substitution of Si by Al atoms.
EXPERIMENTAL
The sorption of the single components and their binary mixtures was
measured in a modified version of the isosteric method developed by Bulow
et a1(1,2) and is fully described in a previous paper(3) The important
feature of this method in the case of mixtures, is the constant composition of
the sorbed phase over the temperature range scanned.
62
12
11
10
.
I
no
-n
5 9
7 ~.
3.0 3.1 3.2 3.3 3.4 3.5 3.6 I
low1
14
12
10
D
3.0 4.0 5.0 6.0 7.0 E.0
lOC/T
Fig.4
Nz-silicalite- 1
isot heriris
Fig.5
1.4
1.2
1.0 Fig.6
.
2
P
b
0.n
0.6
75 mol% N2/25 mol% C 0 2
- NaY isotherms
0.4
0.2
0.0
0 20 40 60 80 100 120 140 160 1
e.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
I
Pressure/kPe Pressure/kPe
25 I Fig.8
Isosteric heat of
sorption. qT. of C02/N2
mixtures in silicalite- I
as a function of mole
fraction, Yco?.of C 0 2 in
gas phase.
5
0.0 0.2 0.4 0.6 0.9
I
1.0
ycor
66
TABLE 1
Henry's Law Constants. K H and Separation Factors a' and a for Sorption of
CO?. N: and CHJ in Silicalite.
Temp I
KH/( 10-6mol.kg.'.Pa-' a' a I
(K) I CQ N? CHj CO:/N2 COI/CH4 C H 4 / N 2 IC@/N2 C02/CHj CHJ/N2
273 I 85.0 4.97 17.0 17.04 4.99 3.43 I -20 3.5 3.5
13.29 4.38 3.04 3.0 2.8
9.44 3.69 2.69 2.7 2.7
5.65 2.81 2.01 2.5 2.2
10.3 2.54 4.31 4.04 2.38 1.69 -4 2.0
TABLE 2
Henry's Law Constants, KH and Separation Factors a' and a for Sorption of
CO,, N2 and CHJ in Na-Y Zeolites
Temp1 a' a
1 50 2 . 5 9 ~10-3 4 . 0 7 10-3
~ I .57
200 0.363 8.37~10-~ 1 . 3 6 ~ 1 0 - ~ 4337 2657 1.63 1.52
247 1 . 9 9 ~ 1 0 - ~1 . 5 0 ~ 1 0 - ~ 2 . 5 0 ~ 1 0 - ~ 1327 795 1.67
270 3.95~ 5.79~ 9.75~ 693 405 1.68
40
+ experimental
3 5 .
-- IAS Theory
30
+ experimental
- 20
: 10
u
30 + experimental
-
.
= 20
-- IAS Theory
0
10
0
70
1.0
-
- 0.6
Ne
0
a
0.6 -
n
I?)
2
Y
0.4 -
a
CH,
0.0
0.0 0.2 0.4 0.6 0.8 1
M o l e Fraction Sorbed Phase (X)
loo
90 f
10
2o
0
0
i
4
40 80 120 160 2 I0
Pressure/kPa
Fig. 13 Isotherms for 75 mol% N2/25 mol% CH4 sorbed at 150K in NaY
(+) experimental versus predictions by Competitive Langmuir, TAS and
Ruthven's Statistical Thermodynamical models.
72
.................................
90 - .... .... t Langmuir
-
80
.+ IAS
0
0 40 80 120 160 0
Pressure/kPa
Fig. 14 Isotherms for 50 mol% N2/50 mol% CH4 sorbed at 150K in NaY
(+) experimental versus predictions by Competitive Langmuir, IAS and
Ruthven's Statistical Thermodynamical models.
;cF
.'
80 -
f'
70 - :
-;
\ 50
60
-
\ - - - - - _ _ _ _ _ _ _ _
m
m 40 - Ru t h u e n
PI
9 30
-
c
20 -
0 4 .~
0 40 80 120 160 200
Pressure/kPa
Fig. 15 Isotherms for 25 mol% N2/75 mol% CH4 sorbed at 150K in NaY
(+) experimental versus predictions by Competitive Langmuir, IAS and
Ruthven's Statistical Thermodynamical models.
73
temperatures the IAS and the Competitive Langmuir model were both
equally good at predicting the experimental isotherms. The root mean
square deviations calculated for all three models for all three sorbed phase
compositions and for all three temperatures are summarized i n
Table 3.
In this Table the very poor predictive ability of the Statistical
Mechanical model compared with the other two models can be clearly seen.
However, this is not surprising since this model is not really designed to
cope with the large number of molecules sorbed per supercage in these
mixtures. In order to cope with the large number of molecules sorbed per
unit cell the unit cells were divided into smaller volumes which contain only
4 molecules at saturation. The model then assumes that there is little
transference from one sub-volume to another and this is a gross
simplification of the actual experimental situation.
TABLE 3
Comparison of the predictive models for nitrogenlmethane mixtures sorbed
Na-Y ________~ - ~~~
REFERENCES
SUMMARY
A study was made on the adsorption of alcohol-water mixtures
on hydrophobic siliceous molecular sieves. The aim of this paper
is to show the concept from the selection of the most effective
structure types over the influence of the Si/Al ratios of the ad-
sorbent.~from template synthesis and the dealumination of Penta-
sils from the “inorganic way’, the selection of a hydrophobic bin-
der to the use of the zeolites in innovative processes.
INTRODUCTION
The novel h l g h silica molecular sieves with distinct hydropho-
bic properties synthesized during recent years make a selective
separation of organic compounds from aqueous solutions possible
(ref. 1). As polnted out by several authors, an industrial poten-
tial is the adsorptive separation of alcohols from ethanol (ref.
2) and butanol-isopropanol (ref. 3) fermentation. I t seems that
adsorption processes are alternative methods for the energy consu-
ming conventional three stage process : strlpplng-rectification-
vacuum rectlfication (ref. 4). The aim of this paper 1s to examine
the thermodynamics of ethanol-water mixtures on hydrophobic sill-
ceous adsorbents for an optimization of the adsorbents properties.
The analysis of the excess isotherms was carried out by the ther-
modynamics of energetically homogeneous and heterogeneous adsor-
bents. Further investigations deal with the selection of suitable
binders for hydrophobic molecular sieves, the characterization of
the desorption step of ethanol from the adsorbents and the use of
the molecular sieve pellets in innovative processes.
THEORY
To describe the liquid phase adsorption of blnary alcohol-wa-
ter mixtures the adsorption excess was used (ref. 5) :
r2e= n2e/ rn = no ( x20- x21 / m (1)
0
The adsorption excess can bedetermined experimentally, when n
76
‘21,min
EXPERIMENTAL
The molecular sieves were calcinated to remove organic com-
pounds, exchanged with 0.1 M aqueous NaN03 solution and washed be-
fore use.
For the determination of the adsorption excess about 0 . 2 g ac-
tivated adsorbens was contacted with about 1 ml of alcohol-water
mixture of known composition. The equilibrium mole fractlon was
determined refractometrically after 48 hrs.
The DTG measurements were carried by means of a microbalance
(Setaram, Lyon) with a controlled linear heating rate of 10 K/ min
and a dried argon stream a t a flow rate of 3 l/h.
TABLE 1
Characterization of the hydrophobic adsorbents used
~~
mole fraction x i
85 117.0 32.1
Nal. 1 (A102)1.1 (‘‘O2) 94.5
50 112.8 33.5
Nal. 9 (A’02) 1.9 (s102) 94.1
40 115.6 33.1
Na2. 3 (A102)2. 3 (si02)93. 7
19 128.4 36.5
Na4,8 (A102) 4.8 (“O2) 91.2
13.5 Nag.6(Alo2)6.6(Si02)8g,4 132.2 42.0
c 02
Si IAI.13
-10 0 10
mMa
-10
Kl:
Si/AI=19
0 10
-
.
Si/AI= 40
U/kJmol”
Si/Al= 50
10 0 10
SilAI.85
-10 0 10
0.1
TABLE 3
(Si/A1IF ratios after modification determined by 27Al MAS NMR
(S i /All
water pressure/kPa
A B C
0 15 15 15
4 20 21 18
13 25 24 26
40 53 27 36
80 64 25 46
tI
20 40 60 80
p(kPa1
TABLE 4
characterization of the Pore volume of the pentasiles modified by
procedure B
I : : ; : : :
1 2 3F4 5 6
Aluminium per unit cell
TABLE 5
Adsorption characteristics of the pelletized pentasil
percent by weight.
The hydrophobic Pellets were sucessfully applicated in the
- removal of ethanol from the gas and the aqueous phase
- separation of alcohols from ethanol and butanol fermentation
- in-situ fermentation of ethanol
- dealcoholization of beer and wine
ACKNOWLEDGEMENTS
The authors are indebted to Dr. W. Reschetilowski for helpful con-
tributions and the group of Prof. Br%uer for numerical calcula-
tions.
REFERENCES
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2 N.B. Milestone, Report NO. C.D. 2355, Methods of Separating
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20 W.-D. Einicke, W . Reschetilowski, H. siegel, J. BBhm and
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v.Szombathely, M. Jusek, H.-R. Poosch, P. Brluer, W.
88
p. 271
25 B.C. Lippens and J.H. de Boer, J. Catal. 4 (1965) 319
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SchBllner and 0. Rademacher, J. Chem. Soc., Farad. Trans. I
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L 15
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G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 89
0 1991 Elsevier Science Publishers B.V., Amsterdam
ABSTRACT
In the first part it is shown both experimentally and
theoretically that the H' NMR chemical shift of surface hydroxyl
groups as measured for strongly dehydrated zeolites by the MAS
technique is a suitable parameter to characterize their strength
of acidity. Moreover, this method allows a direct and unambiguous
determination of the concentration and accessibility of the
various OH groups. In contrast, for hydrated zeolites a
superposition of several effects (e.g. Plank's mechanism,
formation of hydroxonium ions, adsorption of water molecules on
Lewis acid sites) may occur which requires a more detailed
analysis of the spectra and additional information for an
unambiguous interpretation.
In the second part recent results of pulsed field gradient
(PFG) NMR studies of self-diffusion in zeolites are presented
which include xenon self-diffusion, the anisotropy of diffusion
in zeolites, NMR tracer exchange experiments and a critical
comparison of PFG NMR diffusivities with results of other
techniques.
ZOH = 20- + H+
H+ +M = MH+
PhOH
with SH = 3.55; SA1 = 2.22; So = 5.21; Ssi = 2.84 (cf. ref. 4),
is plotted together with experimental values of 6H in dependence
on the silicon-to-aluminium ratio n. The nearly identical
functional dependence of both quantities provides ample evidence
for the usefulness of JH as a measure for the strength of
acidity. In this connection it should be mentioned that due to
the use of CH4 as an inner standard (ref. 3 ) the absolute values
of 6H plotted in Fig. 2 are reduced by about 0.3 ppm with respect
to ref. 5 and that the accuracy of the absolute values of JH has
been enhanced considerably so that the present error does not
exceed ? 0.05 ppm. Moreover it was possible to show by a thorough
investigation that the residual linewidths which limit the
accuracy for a determination of the values of 6H for bridging OH
groups on zeolites are not controlled by artefacts or
imperfections rather than by the distribution width of the
strength of acidity (ref. 6).
92
n-
Fig. 2. Values for the intermediate electronegativity Sm and
the chemical shift bH of the (accessible) bridging OH groups
in dependence on the silicon-to-aluminium ratio n for various
zeolites (HX: zeolite H-X; HY: zeolite H-Y; HM: mordenite;
HE: erionite; HZ: H-ZSM-5).
20 -
+
"iO
A E D ~ /kJrnd-' -
Fig. 3 . Dependence of calculated values for the chemical
shielding aH on calculated values for the deprotonation energy
(ref. 2 ) .
on air
Si
1.65 ppm
3.0ppm 2.0ppm
10 5 0 -5 10 5 0 -5
-61 H ppm -61 H ppm
Fig. 4. H' MAS NMR spectra of carefully dehydrated (200 O C , 10
K/h, lo-' Pa, 24 h) silica (aerosil 200 1 Degussa) and after
keeping it 30 s on air (ref. 11).
S A PO-511 S A PO-512
f b)
'HMAS NMR H
Si O A I
Ibl
SiOH
3630
f/rm-'L- t/cm-1 -
3630
95
i
100
1
0 1 2 3 4 atoms per
24 si (A1 )atoms
0
I . .
2
. .
4
. .
6
. .
8
-
molecules per
24 Si ( A l l atoms
a I 55 ms b
0.2 1
I ’ . ’ ’ ’ . ’ -6,,mSI
0 OD4 a2 0
b I .
0 20 40 60 80 Alms
with <r2 (A)>i and <r2 (4) >l.r. representing the mean square
displacements of the two subgroups, respectively, and with r(A)
denoting the relative amount of the latter subgroup, i.e. the
relative amount of atoms leaving the individual crystallites
during the observation timed. For a discussion of the transport
properties of the zeolite crystallites, an echo attenuation of
the form of eq. (10) contains two types of information: the mean
square displacement <r2 ( A ) >i of the atoms in the intracrystalline
space as obtained from the slope of the second, slower decaying
part of the 1n"f-vs.- J2 plot, and the quantity r ( h ) , resulting
from the relative contributions of the two constituents. Both
quantities are represented in Figs.10~and 11, respectively, in
dependence on the observation time. It is obvious, that the
function r(A) contains the same information as a conventional
tracer desorption curve (ref. 3 4 ) . In previous NMR self-diffusion
studies with methane, in general echo attenuations of the type of
Fig. 9c have been observed (ref. 34). Such a behaviour has again
been found on investigating the methane diffusivities in the
zeolite specimens applied in this study.
TABLE 1
Values for the intracrystalline self-diffusion coefficients Di
and the intracrystalline mean life time ri of xenon and methane
in various specimens of zeolites NaCaA, NaX and ZSM-5 at 293 K
and a sorbate concentration of about 3 methane molecules or xenon
atoms per 24 Si(A1) atoms.
Y c o n t .
45 X 13 1.0t0.3 3.0tl.0 80t2O 1.0t0.3 3.0tl .O 6t2
63 X 20 1.5t0.4 4.0t1.0 45t10 1.5t0.4 4.0tl .O 4t2
80 x 5 1.5t0.4 0.4t0.2 252 8 1.520.4 0.4t0.2 lt0.5
Wax 50 5.0t1.5 8.0t2.O 15t10 20t5 2tl 5tl
20 5.0t1.5 1.5t0.5 5t3 20t5 0.4t0.2 2t1
ZSM-S(a) 25 * O.Pt0.3 11t3 ,40 4tl 3tl 4t1
ZSM-5(b ) 100~30x30 0.Pt0.3 160t40 >70 4t1 45t10 ~ 3 0
mean c r y s t a l l i t e dimension
Diffusion Anisotrovv
Among the problems connected with new zeolite structures, a
possible anisotropy of self-diffusion deserves special
consideration. Since the PFG NMR method allows the observation of
molecular migration with respect to the direction of the applied
field gradient (ref. 3 4 ) which may be easily changed by applying
suitable gradient coil arrangements, favourable conditions exist
for the investigation of diffusion anisotropy. Literature
provides various examples of such diffusion studies with liquid
crystals and membranes where molecular diffusion proceeds in a
well oriented sample of macroscopic dimensions.
A completely different situation exists if one considers
molecular diffusion in crystalline catalysts and adsorbents.
Being of the order of a few micrometers, the diameters of the
individual crystallites are too small to allow the conventional
method of studying diffusion anisotropy. However, also in this
case PFG NMR may provide information about the extent of
diffusion anisotropy. This information is contained in the shape
of the N M R spin echo attenuation versus the gradient intensity,
which in the case of isotropic diffusion yields a simple
108
where the quantities DXX, Dyy and D,, denote the principal
values of the diffusion tensor. The orientation of the field
gradient with respect to the principal axes system is represented
by the angles &and Y .
The quantity
c Y(C)> = -
1 J1exp{- c
471 -1
with
I ( J ) = J2;xp{-c sin22
0
rxgpectively.
Limits of ADwlication
The versatility of the PFG NMR method to study diffusion
processes in zeolites and its successful application to numerous
problems in zeolite science and technology (cf. ref. 42) implies
the temptation to apply it also under such conditions where
110
gaseous C6D6
adsorption vessel
granulated NaX +C6D6
20 mm
glass vial
H - Z S M - 5 .CgH(
-
-
D
Fig. 15. Comparison
of the self-diffusion
coefficients obtained
\ from NMR tracer
\ exchange measurements
\
( 0 293 K; A 386 K)
i\ f\
\
with values
calculated from
sorption uptake
experiments ( o 303
K; 0 363 K; A 393
K) using eq. (17).
Both experimental
f
10Eo 1.0
series have been
carried out with the
same silicalite
specimens.
Loading I molecules per 0.25 U.C.
This exchange process may be directly recorded via the intensity
of the H' NMR signal. It is shown in Fig. 15 that the self-
diffusivities determined from these experiments are in
satisfactory agreement with the results of uptake experiments,
when the relation between the coefficient of diffusion (Dd) which
112
TABLE 2
Comparison of PFG NMR diffusivities with the results of quasi-
elastic neutron scattering and Molecular Dynamics simulations as
well as with the results of macroscopic non-equilibrium measure-
ments (uptake, zero length column, permeation). Data refer to the
limit of small sorbate concentrations, the unit is m2s-'.
Permeation 10.10
334 K
r e f . 69
113
REFERENCES
1 J.E. Bartmess, J.A. Scott, R.T. Mc Iver, J. Am. Chem. SOC.
101 (1979) 6046.
2 J. Sauer, J. Mol. Cat. 54 (1989) 312.
3 H. Pfeifer, Colloids and Surfaces 36 (1989) 169.
4 R.T. Sanderson: Chemical Bonds and Bond Energy, Academic
Press 1976.
5 D. Freude, M. Hunger, H. Pfeifer, W. Schwieger, Chem. Phys.
Lett. 128 (1986) 62.
6 E. Brunner, J. Chem. SOC., Faraday Trans. (in press).
7 E. Brunner, D. Freude, B.C. Gerstein, H. Pfeifer, J. Magn.
Res. (in press).
8 J. Dwyer, J. Dewing, N.E. Thompson, P.J. O'Malley, K. Karim,
J. Chem. SOC., Chem. Comm. (1989) 843.
9 H. Ernst, Z. Phys. Chenie, Leipzig, 269 (1988) 1073.
10 E. Lippmaa, A.V. Samoson, V.V. Brey, Y.I. Gorlov,
Doklady Akad. Nauk 259 (1981) 403.
11 E. Brunner, unpublished.
12 U.M. Mastikhin, I.L. Mudrakovsky, A.V. NOSOV,
Bruker Report 2 (1989) 18.
13 M. Hunger: Thesis (Prom. B) in preD.
14 - .
S. Halik, J.A. Lercher, H. Maver, >. Chem. SOC., Faraday
Trans. 1; 84 (1988) 4457.
15 H. Rosenberger, H. Ernst, G. Sche er! I. Junger,
R. Sonnenberger, 2. Phys. Chemie, Leipzig 263 (1982) 864.
16 D. Freude, M. Hunger, H. Pfeifer, W. Schwieger,
Chem. Phys. Lett. 128 (1986) 62.
17 H. Pfeifer, D. Freude, M. Hunger, Zeolites 5 (1985) 274.
18 M. Hunger, D. Freude, H. Pfeifer, D. Prager,
W. Reschetilowski: Chem. Phvs. Le t. 163 (19891 221.
19 A. Jentys, G. Warecka, M. Derewinski, J.A.' Lercher,
J. Phys. Chem. 93 (1989) 4837.
20 M. Hunger, D. Freude, H. Pfeifer, J. Chem. SOC., Faraday
Trans. in press.
21 V.B. Kazansky, Catalysis Today 3 (1988) 367.
22 J. Fraissard, T.Ito, in: Proc. 5th Internat. Conf.
Zeolites, Naples 1980, Heyden, London 1980, p, 510.
114
V .B .KAZANSKY
N.D.Zelinsky Institute of Organic Chemistry, Moscow, USSR
SUMMARY
The Lewis acidity of cationic forms of zeolites and of those modified by
mild steaming or by Zn and Ga ions was studied using molecular hydrogen and
light paraffins as molecular probes. The extent of their perturbation was con-
trolled by IR diffuse reflectance spectroscopy. It was concluded, that Lewis
sites should be considered not as low coordinated cations, but rather as
acid-base pairs in which the neighboring basic oxygen is equally important.
The role of extra lattice aluminum or modifying Zn and Ga ions in cracking of
paraffins or their aromatization is discussed.
INTRODUCTION
The catalytic properties of zeolites are mainly connected with their aci-
dity. Therefore the central problem of catalysis on zeolites is the nature of
their acid active sites.
The recent information on the Broensted acidity of zeolites is rather com-
plete, since it could be easily followed by such direct spectroscopic methods
as IR or high resolution solid state NMR. On the contrary the knowledge of the
nature and the properties of Lewis acid sites is quite not as full. This is
because they could be investigated only by indirect way by means of molecular
probes with spectral control of perturbation of adsorbed molecules.
For this purpose most often ammonia or pyridine adsorption is used. These
molecules have however very little in common with hydrocarbons, whose cata-
lytic transformations on zeolites are of the greatest interest. In other
words, if adsorbed ammonia is protonated by a Broensted acid site or is stron-
gly bonded by a Lewis site, this does not yet mean, that the adsorbed hydro-
carbons would behave in the similar way.
Another, more principal difference between strong bases and hydrocarbons
consists in the chemical nature of their interaction with Lewis acid sites. In
the case of hydrocarbons or hydrogen the elementary step, which is most often
discussed, is the heterolytic dissociation:
6- 6 +
H--H H- H+
-Me--0- + H --.c -Me--O- ----L -Me--O- (1)
2
Unlike this ammonia or pyridine adsorption results in coordinative binding:
118
(2)
Y3
-Me--0- + NH3 c_) -Me--0-
Thus, the strong bases are the tests only for Lewis sites, whereas the mo-
lecu- lar hydrogen is rather the test for the acid-base ion pairs. Therefore
the conclusions on the nature, the strength and the number of Lewis sites ob-
tained from adsorption of strong bases could not be so simply transferred to
adsorption of hydrocarbons.
Of course the best molecular probes for Lewis acidity are the reactants
themselves. Therefore in the previous studies of aluminum oxide and H-zeo-
lites we used the adsorption of light paraffins or the low temperature adsorp-
tion of molecular hydrogen (refs. 1.2). Below the application of the similar
approach for the investigation of Lewis acidity of zeolites modified by vari-
ous methods is reported.
This is also consistent with the spectra (d) and (el of Fig.1, which show,
that the majority of Na ions bind hydrogen more strongly and exhibit the lar-
ger low frequency shifts of H-H stretching vibrations, while the rest of sodi-
um ions could hold and perturb molecular hydrogen only at higher pressures.
The spectra of hydrogen adsorbed on sodium forms of faujasites are more
complicated (Fig.1, spectra (f)-(h) 1. According to our results (ref.4) they
could be ascribed to H molecules perturbed by sodium ions located in SI; SI,
2
and in SIIpositions. Thus, low temperature molecular hydrogen adsorption
allows to follow both the different sites of sodium ions localization in the
zeolite frameworks and the distribution of ions among these sites.
The important feature of IR spectra of hydrogen adsorbed by sodium forms of
zeolites is the dependence of the line shifts on the type of zeolite frame-
works. In this respect hydrogen behaves quite differently from adsorbed carbon
monoxide (ref.7) which for the same cations exhibits very close shifts for
different frameworks. Thus, the perturbation of adsorbed hydrogen depends not
only on the nature of cations, but also on the type of the zeolite crystal
lattice. This is in consistence with the by-point adsorption of molecular hyd-
rogen, which was earlier supported by quantum chemical calculations for alumi-
num oxide (ref.8).
If this conclusion is also correct for zeolites, then for their sodium
forms the shifts should be dependent on the basic properties of oxygen. This
is really observed experimentally. Indeed, the least basic oxygen is that one
in high silica zeolites, which contain the lowest amount of aluminum in their
framework. This results in the smallest low frequency shifts of H2 stretching
vibrations. On the contrary the largest shifts were observed for NaA zeolite,
which contains the most basic oxygen. However, even in this case the value of
the low frequency shift is only 90 cm-l i.e. is about twice less, than that
for hydrogen adsorbed by acid-base pairs of aluminum oxide (ref.1). Thus,
sodium ions are rather weak perturbing sites of adsorbed hydrogen. This is
consistent with the fact, that contrary to aluminum oxide we never observed
dissociative hydrogen adsorption on sodium forms of zeolites.
Bllralent-catlonlr-~orms_oy_qeoliteq
The IR spectra of hydrogen, adsorbed at 77 K on alkaline earth forms of
mordenite are presented in Fig.2. They contain two bands for Mg and Ca
exchanged samples, but only single bands for the samples exchanged with Sr and
Ba ions.
Such difference could be easily explained by various hydrolysis extent of
these cations.
121
d
Fig.2. IR diffuse reflectance spectra of molecular hydrogen adsorbed at 77 K
on alkaline earth forms of mordenite dehydrated at 720 K. (a)-MgNaM, (bl-
CaNaM,(c)-SrNaM,(d)-BaNaM. The degree of cationic exchange is about 60 %.
Hydrogen pressure is 30 Torr.
hydrogen.
If it is really of the bypoint nature, then the charge and the polarizing
ability of lattice oxygen is also important. In other words the charges of ca-
tions and their dimensions are not the only factors affecting polarization of
adsorbed hydrogen. In addition, for bivalent cationic forms the higher positi-
ve charge results in the partial electron density transfer from basic oxygen
to cations. This decreases both positive charges of cations and those of oxy-
gen in ion pairs and results in smaller shifts of stretching vibrations of ad-
sorbed molecular hydrogen in comparison with which one could expect from the
formal electric charges.
H -
0 0
\ / \ / \ + / \ / \ /
2 Si A1 d Si A1 + Si A1 (31
/ \ / \ / \ / \ / \ / \
Later this mechanism was found to be incorrect, since according to the nu-
merous solid state high resolution NMR data the dehydroxylation of hydrogen
forms of faujasites results instead of formation of lattice Lewis sites in de-
alumination (ref.101. Nevertheless our experimental results on low temperature
molecular hydrogen adsorptioii clearly show, that f o r high silica containing
zeolites dehydroxylation still could occur according to scheme (31 (refs.
2,111.
IR spectra of H2 adsorbed at 77 K on HZSM-5 zeolite preheated in vacuo at
different temperatures are presented in Fig.3. At moderately high temperatu-
res, when dehydroxylation has not yet started (770K) , two bands with maxima
at 4125 and 4105 cm-l are observed (fig.3 (a) 1.
With the increase of the pretreatment temperature and of the extent of sur-
face dehydroxylation their intensity decreases. On this ground we assign these
bands to hydrogen interacting with surface hydroxyl groups. Since the position
of the high frequency band is the same as when hydrogen is adsorbed on silica,
this band could be attributed to the molecules, perturbed by silanol groups.
Then the band with a lower frequency of 4105 cm-1 should be ascribed to hydro-
gen molecules interacting with the acidic bridged hydroxyls with stretching
123
The Lewis sites play here the role of the dehydrogenating active centers,
resulting in formation of olefins. The latter are then transformed by Broens-
ted acid sites into adsorbed carbenium ions, which are involved in chain
propagation via /3 scission and hydrogen transfer reactions.
Since the steaming creates extra lattice Lewis active sites, this favors
the dehydrogenation of paraffins and the generation of adsorbed carbenium ions
at the initial stages of the treatment. At the same time the dealumination al-
so destroys the Broensted acid sites. These two factors do influence the cata-
lytic activity in opposite directions. Therefore after mild steaming the reac-
126
tion rate is increased. It reaches then some maximal value after moderate time
of steaming and goes down for the higher extent of the dealumination, where
the steam treatment results in a considerable decrease of Broensted acidity.
This explains the extreme character of the activity dependence upon the time
of high temperature water vapor treatment.
To check this explanation the special experiments were carried out in which
the cracking of n-hexane doped by small amounts of 1-hexene was studied on
steam treated and on untreated HZSM-5 samples. As one should expect, the cata-
lytic activity of the nonsteamed zeolite and of that one treated in optimal
hydrothermal conditions changed after 1-hexane addition in such a way that
they reached almost the same values. In other words the activity of the stea-
med zeolite became two times lower, whereas for the untreated sample 2-3 times
higher. Dehydrogenating activity of Lewis sites was also confirmed by the
increased H2 yield (by 1.5-2 times) in the cracking of n-hexane on mildly dea-
luminated zeolites as compared with initial H-form. Thus, the role of Lewis
sites in catalytic cracking was independently proved by purely chemical expe-
r iments .
Recently some other examples of modification effects in developing the
strong acidity of hydrogen forms of zeolites were reported (refs. 16-17). For
instance. Lunsford et.al. (ref.16) found, that dealuminated faujasites and
HZSM-20 zeolites prepared such, that they had a minimum amount of extra frame-
work aluminum were relatively inactive in cracking of hexane, which was used
as a test of strong acidity. Upon exchanging La+3 ions into the zeolites, the
cracking activity first increased with respect to lanthanum loading and then
went through a maximum. The authors explained these results by the model of
strong Broensted acidity. It was suggested, that lanthanum ions formed
[La(OH)2Lal+4 or La(OH)+2 species in 6 cages, which were responsible for the
withdrawal of electrons from the framework hydroxyl groups, thus making pro-
tons more acidic. In our belief this explanation sounds rather illogical, sin-
ce hydrolyzed lanthanum species definitely are of the basic character. There-
fore they hardly would increase the acidity of structural hydroxyl groups, but
rather neutralize them. It looks, that the more probable explanation is that
one similar to the already discussed above for extralattice aluminum ions.
According to it the role of dehydrogenating active sites is played by the lan-
thanum-oxygen acid-base pairs, which are the source of olefins, resulting in
the chain carbenium ion mechanism of cracking.
ting active sites, represent the high silica zeolites modified by Zn and Ga
oxides. They are known as active catalysts for aromatization of light paraf-
fins (ref.18) and therefore attract the growing attention of a number of in-
vestigators.
There are rather strong indications that these catalysts are of bifunctional
nature combining the dehydrogenation of light paraffins on modifying oxides
with the consequent aromatization of olefins on super acid Broensted sites of
high silica zeolite. Therefore in our work (ref.19) the dehydrogenating cen-
ters of these catalysts were studied in frames of the similar approach of the
low temperature molecular hydrogen adsorption. In addition the distribution of
modifying oxides was also investigated by means of XPS and by ESR of adsorbed
bulky stable free radicals, which could not penetrate inside the zeolites mic-
ropores.
The most interesting results were obtained for the samples modified by Zn+2
ions. It was found, that both the ion exchange and the impregnation with zinc
nitrate decreased the intensity of the band of bridged acidic hydroxyl groups
with the stretching frequency of 3610 cm-l. In addition a shoulder from basic
ZnOH' groups at 3660 cm-' was observed.
On the other hand, the modification by Zn also resulted in appearance of
several different Lewis sites. This is evident from the Fig.4, where the IR
spectra of molecular hydrogen adsorbed at 77 K on the sample modified by Zn
are represented.
z,'L
+ HI
The important point is, that the largest shift of adsorbed hydrogen consi-
derably exceeded that, which was earlier observed for hydrogen adsorbed on the
surface of the bulk ZnO (ref.20). This means, that the adsorption sites on the
surface of zinc oxide and in high silica zeolites modified by Zn+2 ions are of
the different nature.
This difference could be explained by the different nature of oxygen, which
surrounds Zn+2ions in both of these cases. In the modified zeolites this
could be the oxygen of the zeolite framework, which certainly is different
from that of ZnO. Such interpretation is confirmed by the following experimen-
tal results:
It was found, that the sites, which most strongly perturb adsorbed hydrogen
at low temperature do dissociatively adsorb it at room temperature. This is
evident from the spectrum (c) of the Fig.4, which shows, that after keeping of
modified ZnZSM-5 sample at room temperature in hydrogen and cooling it back to
77 K the low frequency band of adsorbed molecular hydrogen was disappearing.
Instead the growth of the band from the bridged acidic hydroxyl groups with
the stretching frequency of 3610 cm-l was observed.
This could be explained by the heterolytic dissociative adsorption of hyd-
rogen, which blocks the Lewis acid-base pairs and makes them unaccessible for
the adsorption of molecular hydrogen:
+ -
-Zn--0- t H2 - H
-Zn--0-
H
(5)
The explanation of this discrepancy was found, when we studied the chemical
composition of modified samples by XPS .It was found, that the external surfa-
ce of the zeolite micrograins was markedly enriched in Ga, whereas Zn ions
were distributed homogeneously inside the zeolite micropores. Therefore the
lack of IR observation of Lewis acid sites for gallium doped samples should be
explained by their low concentration inside the channels.
130
We observed these low coordinated gallium ions on the outer surface of zeo-
lite micrograins by more sensitive ESR technique. As a molecular probe the ad-
sorption of 2.2.6.6 - tetramethylpiperidine 1-oxyle stable free radical was
used, which due to its large dimensions could not penetrate inside the zeolite
micropores. The ESR spectra of this free radical exhibited the hyperfine
splitting from low coordinated Ga ions, which proved their existence on the
external surface of micrograins of modified zeolite (ref. 1 3 ) .
CONCLUSIONS
The increase of activity in transformations of paraffins after mild stea-
ming or modification of zeolites by various oxides is usually connected with
formation of some new super acidic Broensted active sites (ref.13,16,21).
The present paper supports an alternative explanation,according to which
the main effect of modification consists in creation of Lewis acid sites. In
the steam treated samples their role is played by extra lattice aluminum. It
is shown, that such active centers could dehydrogenate paraffins and in this
way assist the easier formation of adsorbed carbenium ions. This results in
higher reaction rate of cracking.
In the case of catalytic transformations of light paraffins to aromatics
the role of dehydrogenating Lewis sites is played by modifying Zn and Ga ions.
They differ in their location, since the former are homogeneously distributed
inside the zeolite micro grains, whereas the latter are mainly localized on
their outer surface.
It was also shown, that the Lewis active sites should be considered as
acid-base pairs, where both low coordinated cations and the neighboring basic
oxygen of the zeolite crystal lattice are equally important. The best molecu-
lar probes for their study are molecular hydrogen and paraffins, i e. the sub-
strates, which are involved in catalytic reactions with participation of such
active sites.
REFERENCES
Hellmut G. Karge
Fritz-Haber-Institut der Max-Planck-Gesellschaft Berlin, 1000 Berlin 33, FRG
A €3STKACT
Methods of identification of various acidic sites in zeolites (Brensted sites, different
types of Lewis sites, cations) are briefly reviewed. Similarly, techniques for deter-
mination of the density of acid sites are discussed and illustrated with selected
examples. In particular, a good agreement between the results obtained by IR (using
pyridine as a probe molecule) and ESR (employing NO) in determining Lewis site
densities of, for instance, progressively dehydroxylated H-Y is demonstrated. Emphasis
is laid on the discussion of techniques, such as titration, in aprotic solvents, IR with and
without probe molecules, 'H MAS NMR, temperature-programmed desorption and
microcalorimetric measurements of heats of adsorption of basic probe molecules, which
are suitable for characterising the strength of acidic sites. Quantitative evaluation of
TPD spectra using a kinetics model as well a s the combination of different methods is
described in more detail, and results obtained by various techniques on selected
examples of acidic zeolites are compared.
Most of the important reactions carried out over zeolite catalysts are acid-catalysed
even though there is a n ever increasing interest in zeolite catalysis on basic sites [ l - 2I.
The term "acidity of zeolites", however, is by no means unequivocal. "Acidity" could
designate (i) the nature of acidic sites (e.g. Brcdnsted sites 131, various forms of Lewis
centres such a s "true" Lewis sites [4-5], cations), (ii) the number or density of the
respective sites or, finally (iii) their strength. Although there exists a n overwhelming
evidence that a t least for the large majority of acid-catalysed reactions the acidic
Brplnsted centres of zeolites (acidic hydroxyls) are the relevant active sites [6-10!, there
is still a debate on the role of the Lewis centres [ll-191 in zeolite catalysis. In any event,
there i s no severe difficulty to discriminate between the various types of acidic sites. A
survey of the most relevant methods of distinguishing the various types of acidic sites is
presented in the first section. In fact, this can be rather brief since a number of
excellent earlier and also more recent review articles are available which cover this
subject [8, 20-231. Similarly, the determination of the relative or absolute density or
number of acidic sites will not be dealt with in great detail. Most of the techniques
suitable for identifying the nature of the acidic sites can be developed in such a way
that they provide quantitative information. Thus, in the second section some of the
important methods for quantitative evaluation of acidic sites in zeolites will be pre-
sented and for a few instances the results ofdifferent techniques will be compared.
134
A more difficult problem concerning the acidity of zeolites is the evaluation of the
acidity strength. Indeed, more recently some theoretical concepts have been developed
to rationalise the acidity strength of Bransted acid sites in zeolites [24-321.
They relate acidity strength to long range collective phenomena and/or more
localised effects of structure and chemical composition. Hence, theoretical ideas such a s
"activity" or "efficiency" (regarding the zeolite as a crystalline liquid, see Refs. [241,
[27]), Sanderson electronegativity (see Refs. [25],[261, [281, [301), topological densities
(see Ref. [31]), quantum mechanical effects of bond lengths and angles (see Ref. [291)
and deprotonation energies (see Refs. [29], [32]) are involved. Detailed discussions of
these concepts were presented by Dwyer [221 and Rabo and Gajda [231.
There is, however, an urgent demand to have a t hand reliable techniques which
enable us to characterise and measure the acidity strength of zeolite materials, not only
to verify or falsify theoretical concepts, even though this is certainly a n important
point. Progress in experimental techniques will extend the data base for further im-
provement of theoretical approaches to the phenomenon of acidity strength. A practical
need is felt to determine the acidity strength experimentally in a reliable manner, since
in many instances i t has become quite obvious that not only the number but also the
strength of acidic sites is particularly decisive for the behaviour of zeolitic materials in
sorption and catalysis (see, e.g. Refs. [331, [341).
Quite a number of methods have been suggested, developed and employed to
characterise the strength of acidic sites in zeolites. In the third part of this contribution
a n attempt is made to evaluate some of the more important ones and to illustrate them
by pertinent examples taken from the literature or own measurements. Special
emphasis is laid on the comparison of results obtained for one and the same acidic
zeolite sample by the use of different techniques for the determination of density and
strength of acidic sites.
TABLE 1
0 Lewis ?AI
(framework) IR + probes [201
AIO +,[AI,0y](3X*21 27AlMAS, 15N NMR [39.411
Al-oxides ESR + probes [65-671
(extra-framework)
Other oxides
Cations, Men +
I IR + probes
Regarding the methods to distinguish between the various types, i t has been claim-
ed several times that Hammet indicators are non-specific whereas aryl indicators
should indicate only Bransted but not Lewis sites [36].This, however, was disproven
[37-38,76-771. It was shown by Karge [37]via U V M S transmission spectroscopy that,
for instance, triphenyl methanol, @,C(OH), reacts with a surface being free from
Bransted sites as well, giving the typical spectrum of @,C+ carbenium ions.
The most powerful and widely employed techniques for discrimination of acidic
sites are the IR and NMR spectroscopy used with or without probe molecules [a,20,39-
431.Acidic OH groups may be detected by the position of the corresponding OH stretch-
ing vibration in the range of ca. 3520 to 3650 cm-l [8,9, 20, 441 or by their typical
chemical shift in 'H MAS NMR [41,421. Adsorption of probe molecules on acidic OH'S
gives rise to characteristic features in the spectrum which also reveal the presence of
Bransted sites. Thus, after interaction with pyridine, typical bands stemming from ring
deformation modes occur a t 1632 cm-' ( w 8a) or ca. 1540 cm-l ( v 19b). Reaction with
ammonia results in the appearance of the v,(NH4+) band around 1445 cm-l. Similarly,
adsorption of 15N-pyridineon acid Bransted sites causes a chemical shift of S = 171-174
ppm vs. solid NII,NO, [39-401.
27Al MAS NMR allows for the determination of the number of A1 atoms tetra-
hedrally coordinated in the framework, Al'. Since tetrahedrally coordinated A1 corre-
sponds (in zeolites not modified via dealumination) to the presence of Bransted acid
sites, this provides another means to indicate those centres [431.
True Lewis sites (i.e. Al-containing species on extra-framework sites, AINF, [4-5,
35, 451)as well as cations can be identified via IR spectroscopy with the help of suitable
probe molecules such as NH,, pyridine, acetonitrile or CO. Ammonia molecules coor-
dinatively bound to true Lewis sites and I or cations give rise to a broad band around
136
1620 cm-l. The u(19b) band of pyridine attached to Lewis sites is usually more intense
and sharp bands occur around 1450 cm-I for true Lewis sites and in the range from 1440
to 1551 cm-l for cations depending on their Coulomb field [20, 46-47]. Similarly, the
band position of adsorbed acetonitrile and CO is affected by the nature (e/r) of the
respective cation [ 37,48-491.
In the case of IR spectroscopy usually only one type of Al-containing extra-frame-
work species is indicated by the probe, i.e. with pyridine just one band appears a t 1452
cm-l. Only in a few instances a doublet (1456,1451 cm-l) was observed [45,50]. In con-
trast, 27A1MAS NMR frequently reveals the presence of different types of extra-frame-
work Al. In fact, the interpretation seems to be difficult; however, besides octahedrally
coordinated extra-framework A1 also penta- and even tetrahedrally coordinated species
are being discussed [41,43,51-531.
'ABLE 2
Method Remarks -
Ref.
Those methods which are reliable in discriminating the various types of sites (e.g.
IR spectroscopy, '13 NMR, 29Si and 27Al NMR spectroscopy) can be in most cases em-
ployed for quantitative measurements as well.
137
In this context, i t should be mentioned that the NMR techniques provide the abso-
lute numbers of sites, n (sites), under investigation in a very straight-forward manner,
uiz. by the area of the respective signals. In contrast, the bands of IR absorbance, which
are typical of certain acidic sites, must be evaluated with the help of the appropriate
extinction coefficients according to
n (sites)= 1;'vdv
I
where E, d, v1 and w2 are the extinction coefficient, thickness of the sample, beginning
and end of the particular band, respectively. The extinction coefficient must be deter-
mined in an independent experiment (see, e.g. Refs. [54-561 ) and may depend on the
coverage of sites. However, in many cases i t is sufficient to use relative densities to
obtain the relevant information about the relationship between numbers of sites and,
e.g. catalytic or adsorption properties [9-10,201.
Figure 1 illustrates the application of IR spectroscopy and 'H NMR spectroscopy on
the determination of the number of Bronsted sites, respectively [3,57-581.
W
U
= 48.8 0Hh.c.
3670 3580 cm-' bridgin
acidic 08s v]
= 49.2 0Hh.c.
z
a
c
-
-
t-
5
wl
z
a 'I
z 7 4,s 2
I-
! E
I
I(1) IR-SPECTROSCOPY
J.E. Uytterhoeven. 1. G. Chrirtner and W. K. Hall
I ~ H
M A S N M R SPECTROSCOPY]
H.Pfeifer, D. Freude and M. Hunger
1. Phyr.Chem.69(1965)2117 Zeolites 5 (1985) 274
(2) J.E. Uytterhoeven. P. Jacobs, K. Makay and
R. Schoonheydt
1. Phyr. Chem. 72 (1968) 1768
Fig. 1 Determination of bridging acid OH groups in HY (90) by IR and 'H hIAS NMR.
Most of the other techniques indicated in Tables 2 and 3 suffer from certain restrictions.
With respect to the titration method, this will be elucidated in the third section. Deter-
138
mination of the ion exchange capacity, e.g. with NH4+, gives usually a good estimate of
the upper limit for the total number of acidic Brernsted sites, however, often even very
weak sites are involved, without any relevance to catalysis.
Adsorption and desorption of probe molecules requires, inter alia, t h a t only one
type of sites exists in the zeolite, otherwise the assignment of the amounts of adsorbed
or desorbed probe molecules might be erroneous. In such cases, where more than one
type of site is involved, the combination with IR and/or NMR measurements is
advisable [59-611. Finally, the evaluation of sites via the rate of suitable test reactions
is well established for a series of homologous zeolite catalysts [34,62-641. Comparison
of quite different types of zeolites could be misleading. This field, i.e. application of test
reactions for determination of density of active sites is not yet satisfactorily explored.
As already pointed out (see also Table 3), it is possible to identify and quantitative-
ly determine acidic Lewis sites by IR spectrosopy with the aid of suitable probe mole-
cules such as pyridine, ammonia, carbon monoxide and hydrogen. The direct measure-
ment of Al-containing extra-framework species (true Lewis sites) can be achieved via
27Al MAS NMR,provided the Al-content is not too low [43,53].
TABLE 3
absolute numbers)
0 27AIMAS NMR Requirements:A1 content not too low, 1431
Spectroscopy all Al observable (area of respective
signal)
0 29Si MAS NMR Combined with chemical analysis [91l
0 ESR Spectroscopy NO adsorption [65-681
However, ESR spectroscopy using NO as a probe, provides also a valuable tool not
only for identification but also for quantitative evaluation of Lewis sites in zeolites.
This was first shown by Lunsford et al. [65-671, see also Ref. [591. Figure 2 shows a n
ESR spectrum obtained after adsorption of NO on a n H-ZSM-5 sample [68]. It is almost
identical with the ESR spectrum of NO adsorbed on alumina [66-671. Double integra-
tion provides the spin density as a measure of the density of Lewis sites.
In a series of experiments, these densities were determined as a function of pre-
treatment temperature. As expected, the density of Lewis sites increases with pretreat-
ment temperature as a result of increasing dehydroxylation 1681. This is indicated in
Figure 3 by the corresponding increase of the spin density of NO adsorbed. In a parallel
139
set of experiments the Lewis site density was determined through IR measurements of
the intensity of the 1452 cm-’ band after pyridine adsorption. Figure 3 demonstrates
that the results of both techniques are in very good agreement.
r
I : : ) p(N0) = 50Pa
lo’* I 1
Adsorbent : H - ZSM - 5 (2) CAZ 49
3. Part = 10-5pa
Tad (Py) = 475 K (2h)
Tdel (Py) = 475 K (1 h)
z Tad(NO) = 298K ( l h )
- 0.6
a
W
n
m
- 0.3
0 I
600
I
700
1
800
I
900
I
1000 1100
10.0
A C T I V A T I 0 N T E M P E R A T U R E [K]
Fig. 3 Density of Lewis sites of H-ZSM-5 (2) or CAZ 49, measured through NO (ESR)
and pyridine (IR) adsorption
140
TABLE 4
correlation between the degree of exchange of N a + against NH4+ (or H') and the
efficiency of thus created acidic hydroxyls. This enabled them to define a n efficiency
coefficient in analogy to the activity coefficient of electrolytes. In the case of H,Na-X
+
(Si/Al =1.23 or Al / [A1 Si]=0.45) this coefficient was u,=0.16 whereas for Y-type
+
zeolite, H,Na-Y (Si/Al = 2.43 or A1 / [A1 Si] = 0.29),a, = 0.6 was obtained. This was the
first evidence for a (collective)effect of the Si/Al ratio on the acidity of zeolites (compare
also Ref. [241).
TABLE 5
TABLE 6
Method Remarks -
Ref.
Even though the method was subject to frequent criticism [78-791, the agreement
between the total number of acidic sites (H, 2 -3.0) and the same number evaluated,
for instance, from the stoichiometry seems to provide some confidence in its reliability.
However, i t turned out that the procedure was obviously not applicable to other zeolite
structures such as mordenites [75-77,80411. The reason is not, as has been often
claimed, that the bulky indicator molecules cannot penetrate into the channels or pores
of structures other than faujasite [23,82]; mordenite for instance, is a large-port zeolite
with twelve-membered rings as pore openings very similar to faujasite. Moreover, it i s
questionable whether slight colour changes of indicator molecules inside the pore
structure would be detectable by the eyes of the experimentalist. However, the main
reason for the failure of the titration method in the case of many zeolites seems to result
from a very strong interaction of the solvent molecules with the acidic sites.
I I
3680
Y
U
z
U
I-
-
I-
I
VI
z
4
L*
+
In the pore system of mordenite the replacement of the solvent molecule by the titrator
base (e.g., butyl m i n e ) is thus severely impeded. This is demonstrated by Figures 4
and 5 which contrast the different behaviour of H,Na-Y and H,Na-MOR in a titration
experiment followed in-situ by IR. Thus, one has to state that, regardless of other
difficulties, the method fails when applied to acidic zeolites such as mordenite, erionite
etc. This is in agreement with the above-mentioned findings [75-77,80-811.
143
V- a v- -a
a afterdehydrationat 725 Kand 1O'Pa d after dehydration at 1 2 5 K and 10 5 Pa
b after admiwon at solvent. CCI, b after admiwon of ~ o l v e n l CCI.
. b after admission of solvent CCI.
c after 1st mje(tion of n butylamine c after 2nd mjeamn of n-butylamme c atterlnd mjert~onof n-butylamlnc
( 0 25 m mol q 11, 8 h 1025mmol (I-) t 2 h
I I
3800 2800
WAV E N U M B E R [cm-'1
Fig. 5 Interaction of solvent (CCI,) with acidic OH groups of H,Na-MOR and in-situ
titration with butylamine
-
trum of the acidity strength distribution was obtained as is shown in Figure 6.
-
Y'
1 very strong H, c-8 2
0 2- strong -82<H0(-56
€ 3 3 medium -5.6 < H, 6-3.0
E
Y
L rc-cl weak -30< H, < 1 5
VI 5 very weak 1 5 < H, < 3.0
Y
+
m 2
-
0
U
a
LL
0 '
*
-
I-
VI
z
u o
HNaY BeNaY MgNaY CaNaY SrNaY BaNaY LaNaY
Figure 7 demonstrates that only the fraction of the strongest sites (Ho 5 -8.2)correlates
with the rate of conversion of the test reaction, viz. disproportionation of ethylbenzene
MI.
D E N S I T Y O F V E R Y S T R O N G A C I D SlTES(H,<-8.2) [mmol.g-1]
desorbs. Therefore, several efforts were made by, for instance, V. V. Yushchenko e t a!.
[85], Dima and Rees [87], Hashimoto et al. [88] and Karge and Dondur [891 to evaluate
in a more quantitative manner the TPD spectra and/or to combine TPD with other
methods, such as IJi spectroscopy, to identify the types of sites releasing the probe
molecules.
Figure 8 displays, as an example, TPD spectra of ammonia desorbing from two dif-
ferent H-ZSM-5 samples, i.e. H-ZSM-B(l) or CAZ 36 and H-ZSM-5(2) or CAZ 49.
I I I I
T E M P E R A T U R E [K]
Fig. 8 TPD of ammonia from two different H-ZSM-5 samples, CAZ 36 and CAZ 49
.lo ’ I 1 I I I I I
-
w
n.
104
I
CATALYST : CAZ 36
0.4 - 1
mz
ao
ul
W
n
A C T I V A T I 0 N E N E R G Y 0 F D E 5 0 R P T I 0 N [k 1 m o 1’1
3
ul
W
n
A C T I V A T I 0 N E N E R G Y 0 F 0 E S 0 R P T I 0 N [k J . m o I ’1
this case the change of the partial pressure of the desorbing species (monitored by MS
or G C ) and the change in intensity of the corresponding adsorbate IR bands, both a s a
function of temperature are simultaneously measured [80,86,921. The peak maximum
in a TPD spectrum of ammonia desorbing from Bransted sites of a zeolite should, for
147
instance, correspond to the maximum change in the intensity of the ammonium ion
band at 1445 cm I . An example for such simultaneousTPD-MS and IRmeasurements is
shown in Figure I I .
Tart. = 670 K
1450 cm-l
01
6 - S I T E S (11)
I I I
400 500 600 700 800 Fig. 11 Combined IR and MS during
T E M P E R A T U R E 0 F D E S 0 R P T l O N [K] TPD of NH, from hydrogen mordenite
I
1 I I I I I I I I
-
r
I
.
I-
A
-
0
r
-
-
Heating rate : 5 K . min-1
0.000 I I I I I I I I I I -
90 120 150 180 210
T E M P E R A T U R E [K]
Fig. 12 TPD of N O from two different H-ZSM-5 samples, CAZ 36 and CAL 49,
monitored by ESK
148
Microcalorimetric measurements
There are only a few research groups applying microcalorimetry to characterise
and compare acidity strength via the differential heat of adsorption, even though this
technique provides in a very clear-cut manner quantitative data for scaling the
strength of acidity. However, the technique requires very careful experimenting and is
frequently somewhat time-consuming. Important contributions came from the groups
of Auroux e t al. [59,94-971, Klyachko et al. [98-1011, Thamm et al. [102-1031, and
Khvoshchev et al. [ 1041.An example taken from a study of Klyachko et al. [981is shown
in Figure 13.
50
1 3 5 7
C O V E R A G E [mmol 9-11
Fig. 13 Differential heat of adsorption of NH, on mordenites (after Klyachko et a]., ReT
1981)
149
IR spectroscopic measurements
IR spectroscopy is sometimes employed a s a sole method for determination of
acidity strengths of sites, in other words, not as a technique complementary to other
ones (vide supra). Thus, it was claimed that the band position (wavenumber) of the OH
stretching band of acidic OH groups is a measure of their strength. This was first dis-
cussed by Barthomeuf [24] when comparing different zeolite structures in the hydrogen
form; see also Refs. [26-28,1061. However, one has to be aware of the fact that other
factors, such as the environment might affect this band position as well, i.e. without
any significant relationship to the acidity strength. Most prominent examples are
positions of the high and low frequency bands of OH groups in the faujasite structure.
Their accessibility for more bulky probe molecules differs remarkably but not, in fact,
their strength [107]. I t seems to be even more dificult to rely on the small shifts of the
OH bands caused by slight but systematic variations of the acidic properties within a
homologous series of zeolite samples. An example is presented in Figure 14 (see Ref.
[47]) for a series of mordenites (see also Ref. [621).
Even though TPD measurements seem to provide support [62,801,the author
hesitated to interpret the small but systematic shift in the OH band positions as being
indicative of decreasing strength of Brflnsted sites in the sequence from H-MOR
through to Ba-MOR. As mentioned earlier, the OH stretching band of acidic OH groups
150
covers, without any doubt, a whole spectrum of sites with a more or less broad distribu-
tion of acidic strengths (vide supra). The fraction of sites falling into certain ranges of
strengths with corresponding OH modes may vary and, therefore, their super-
imposition may lead to shifts in the overall position of the envelope OH band.
I
3600 3580 3615 3605 3616 3618 3620 3620
3800-3400 3612
cm
W a v e n umber
An estimate of the strength of the acidic sites can be obtained from the shift of the
OH bands of the acidic hydroxyls upon interaction with suitable adsorbates such a s
benzene [28,1081 or CO [1091. The resulting shifted bands, however, caused by hydro-
gen or II bonding, are usually relatively broad and do not reveal more subtle differences
in acidity strength. Sometimes the observed shifts may provoke an overestimation or
the differences in acidity. This seems to be so with the results obtained with two
II-ZSM-5 samples (CAZ 36, CAI, 49) a s the comparison with TPD and microcalorimetric
data reveals (see Table 7).
Similar experiments were carried out in the U V M S region by Naccache e t al.
[110] using aromatic probe molecules.
The strength of Lewis sites, i.e. more specifically cations as electron pair acceptor
sites, can be reliably scaled by the shift of the bands of, for instance, pyridine, nitriles
or CO coordinatively attached to them. Examples are provided in the work by Ward
[20,46], Angel1 e t al. 148-491 and Karge [37,47].
151
TABLE 7
COMPARISON OF MEASUREMENTS OF ACIDIC STRENGTH
Test reactions
A few studies attempted to employ test reactions not only to characterise the
density of acidic centres but also their strength [112-1143. The basic idea was that
different acid-catalysed model reactions may require acidic sites of different strengths
which would enable us, conversely, to characterise the strengths of catalytically active
acid sites in zeolites by the rates of a suitable set of model reactions. Thus, i t has been
152
pointed out, for instance, by Weitkamp [112] that isobutane alkylation by butene over
rare earth faujasite-type zeolites requires stronger sites than butene oligomerisation
and this, in turn, occurs on sites stronger than those necessary for butene isomerisa-
tion. Similarly, Karge e t al. [62,113] found, with regard to the required strength of
sites, the sequence dealkylation of ethylbenzene > disproportionation of ethylbenzene
> dehydration of cyclohexanol.
In a more recent study, Guisnet and co-workers [1141 used the following set of test
reactions: isomerisation and cracking of: ( l ) , n-hexane ( a t 673 K); (2), 2-methyl pentane
( a t 673 K); (3), 2,4 dimethyl pentane ( a t 623 K); (4), 1,2,4 trimethyl pentane (at 625 K);
isomerisation and disproportionation of: (51,o-xylene (at 623 K);(61, 1,2,4-trimethyl
benzene ( a t 625 K) and (7), 3,3-dimethyl 1-butene ( a t 473 K).The reaction rates were
extrapolated to 625 K.
Their results suggested t h a t the required strength of the acidic sites, catalysing
these reactions, decreases in the above sequence from (1)to (7).
I t appears that this approach could be further developed and may provide another
possibility of scaling the acidity strength of sites quantitatively through the activation
energies of a set of suitable model reactions.
CONCLUSIONS
While well-established techniques are available for identification of acidic centres
in zeolites and quantitative determination of their density, improved methods are still
required for characterisation and reliable measurement of acid strength and strengths
distribution. For this purpose, temperature-programmed desorption (TPD) of suitable
probe molecules seems to be appropriate provided that possible experimental sources of
error (limitations in mass and heat transfer, effects of geometrical arrangements, etc.)
are avoided. In this case, evaluation of the TPD data on the basis of a valid kinetics
model may provide quantitative results such a s number of types of sites involved, frac-
tional population of these sites, activation energies of desorption (Ed,,), and distribu-
tion of Edes. However, in order to identify the nature of the sites from which the probe
molecules desorb complementary experiments (such a s IR or 'H MAS NMR measure-
ments) are necessary. TPD of NO, monitored by ESR, seems to offer a valuable tool for
characterisation of Lewis sites.
Microcalorimetric measurements of the heat of adsorption released by sorption of probe
molecules onto acidic sites is a very attractive way to quantitatively determine their
strengths. However, analogous to the case of TPD, complementary measurements are
required to assign the calorific data to the types of active centres involved.
Correlating of the rates of a suitable set of test reactions to the strength of the cata-
lysing acidic sites is an attractive alternative. This method deserves further develop-
ment since it could provide a relative simple and fast technique which does not require
sophisticated equipment.
153
ACKNOWLEDGEMENT
Contributions from colleagues, in particular from Dr. Vera Dondur, Prof. Dr. Richard
Fiedorow, Dr. Linda Jozefowicz, Dr. Jurgen Ladebeck, Dr. Jurgen Schweckendiek a n d
Dip].-Phys. Frank Witzel are gratefully acknowledged. The author is indebted to
Dipl. Phys. Uwe Hartel, Mrs. Erika Popovic and Mr. Walter Wachsmann for excellent
experimental assistance.
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156
D. BARTHOMEUF
Laboratoire de RCactivitC de Surface et Structure, URA 1106, C.N.R.S., UniversitC P. et M.
Curie, Paris, France
ABSTRAm
The paper presents correlations between the acidity and the basicity of zeolites. Basic sites are of
the Broensted or Lewis type. The last ones which occur the more frequently consist of the oxygen
atoms of the framework. The charge on the oxygen, which gives information on the basic strength,
can be calculated and the basicity can be experimentally measured using for instance pyrrole as a
probe molecule. Several parameters are identified as affecting the basicity. They are the
electronegativity of the framework atoms, the bonds angles and bond lengths, the structure ionicity,
the crystallographic sitting of the oxygen, the location of Al (pairs, Al gradients). The properties of
basic zeolites in adsorption and catalysis, their resistance to poisons, are presented in relation with
their basicity.
INTRODUCTION
For many years the attention on the main chemical properties of zeolites has been focussed on their
acidity which gives rise to a large number of applications in acidic catalysis. Little has been
published on the zeolites basic properties and on their applications in catalysis and adsorption (1-5).
It is well admitted that Broensted acids and bases are conjugated and that weak acids have strong
conjugate bases and reciprocally strong acids have weak conjugated bases (6). The existence of
protons in zeolites has to be associated with that of basic sites. The paper will consider the factors
which characterize the number and strength of both sites. It will not consider the case of cationic
framework which are not known presently, but it will focus on the family of (Si-AI) zeolites giving
reactions typical of basic centers. One of the first reaction tested in that sense in the side chain
alkylation of toluene with methanol (1,2) which is favoured on basic zeolites over the ring
alkylation catalyzed by acids. The catalysts are X type faujasites i.e. materials with a high A l
content and exchanged with Rb and Cs in the alkaline cation series. Dehydrogenation of
isopropanol is also favoured on the same type of catalysts (7).
158
The study of protonic and non protonic acidity of zeolites has been the subject of very important
research. The Lewis acidity arises from Al or other cationic species, alkaline, alkaline earth or other
cations. In a similar way the basic sites may be considered of the Broensted or Lewis type. The
first one consists of basic OH groups and the second of the framework oxygen atoms. The charge
on these oxygen determines their strength. Some major differences have to be noted specifically for
zeolites in the characteristics of the acidity and of the basicity. Considering first protons, their
theoretical number is equal to the number of AlOb tetrahedra whose charge has to be neutralized,
i.e. to the A1 content. It is also accepted that their strength increases as the A1 content decreases.
The protons are mobile, jumping from oxygen to oxygen and may approach the reactant to form a
cxbocation. The number of Lewis acid sites (extraframework Al or compensating cation) depends
on the zeolite pretreatment for the Al or on the degree of cation exchange for the other cations. For
basic zeolites, most of the samples used do not contain much Broensted basicity, but mainly Lewis
basicity. The number of potential basic sites is equal to that of oxygen atoms in the framework. The
difference from one zeolite to the other is determined only by the charge on the oxygen, i.e. by the
basic strength and by the degree of heterogeneity of the charge distribution, some oxygen being
possibly more basic than others due to different bond angles and bond lengths. In addition and by
contrast with the protons these framework oxygen are not mobile and the reactant has to adjust
itself to the structure geometry which may induce structural selectivities in adsorption and catalysis.
A large number of studies, experimental (8) or theoretical (9) have been devoted to the
characterization of the acid sites, number, strength and location. The calculation based on the
principle of the equalization of the Sanderson electronegativity of the atoms constituting a
compound (10) gives an approach of the average charge on the proton (1 1) or on the oxygen
(1 2,13). The intermediate electronegativity of a substance. Sint. gives the mean electronegativity of
the atoms of the compound, which is the same for all of them. It suggests to rank the zeolites
according to their Sinl value. The results depend in fact only o n the chemical fomiula and not on
structural parameters. It will be shown funher that some advantage may be taken from this.
Acidity
The known increase in protonic acid strength with decrease in A1 content is exemplified in figure
1, curve a, giving the charge on the proton calculated from Sin1 (10,ll). The acid strength can also
be decreased by exchange of a part of the protons by metallic cations, the stronger sites being
exchanged first. It is also well accepted that these results obtained by considering Sinl values give
only trends. Each zeolite structure and topology will superimpose other specific parameters.
159
Basicity
The paper is focussed mainly on Lewis basicity since the oxygen atoms exist in all the zeolites
frameworks. The Broensted basicity is less often present and in addition some OH may be
amphoteric which makes the study less clear (14). The Lewis base strength can be calculated or
determined experimentally.
i) Theoretical approach
Several methods can be used. Ab initio quantum chemical calculations have been applied to
small clusters (15.16). The use of the Sanderson electronegativity equalization principle (10) gives
an overage oxygen charge value. Curve b in figure 1 reports as a function of the A1 content the
average charge on oxygen for a protonic zeolite. The oxygen charge decreases as the zeolite
contains less Al, i.e. as the charge on the proton rises. This is in line with the concept of conjugated
acid-base pairs (12). One may at that point wonder how the material keeps its electrical neutrality
with a constant number of theoretical basic framework oxygen. It has to be kept in mind that
zeolites are oxyacids. Their formula can be written as T On (OH), by analogy with other oxyacids
such as CI On(OH), (12,17). In zeolites m expresses the Al atomic fraction i n the framework and
consequently the average number of protons per TO2 tetrahedron (n + m = 2). The fomiula for a
theoretical fully protonic X type zeolite (AI/AI + Si = 0.45) is T01.55 (OH)o.45. For a ZSM-5
material with AI/AI + Si = 0.04 (Si/AI = 24) it is T01.96 (0H)o.w. It is known in oxyacids that the
acid strength of the proton increases with n (18), i.e. with the number of oxygen free of protons.
This is in agreement in zeolites with the higher acid strengths at the lower Al contents, i.e. lower m.
The framework negative charge which compensates the positive charge of all the protons is shared
between a larger number of oxygen free of protons at low content, i.e., at high n. The charge bom
by each individual oxygen then decreases and the electrical neutrality is maintained.
The calculation of the average oxygen charges of zeolites fully saturated with alkaline cations
using the same Sanderson approach is reported in figure 1 (curves c to g) as a function of the Al
content. The change in oxygen charge as a function of cations electronegativity is given in figure 2
for different Al contents which correspond to usual zeolites compositions (X, Y,L, mordenite, beta
and ZSM-5). Both figures 1 and 2 show that the higher basicity strengths are obtained at high Al
content and low cation electronegativity. The lowest oxygen charge is obtained for the H forms.
Besides the chemical composition other parameters may affect the charges and their distribution in
the framework. It has been shown for a long time that the charge on the oxygen is larger as the
TOT or OTO angles are narrower and as the TO bonds are longer (19). Then the charge on oxygen
depends on the structure and in a given structure on the oxygen crystallographic site considered (4
types in faujasite, 10 in mordenite, 26 in ZSM-5). The introduction in a framework of elements
other than Si and Al will change not only the electronegativity but also the bond angles and bond
lengths and very likely the charge on the oxygen. For instance the replacement of Si by Ge in an X
zeolite increases the measured oxygen basicity (20) while the simultaneous rise in Sint value would
suggest a lowering of basicity. One may expect that the presence of other elements like B, P or of
all the elements known to exist in S A W S , MeAPSO's and EIAPSO's materials also generates very
160
-&1 62
n
E J
aJ 0.4
m 0.4 7
m
%
X ru
0
0
r 3
0
0.3 0.3
aJ %
n
m
L 1
0
m
r ln
u 0.2 lD
0.2 7J
0.1
0 0.1 0.2 0.3 Al/Al + S i
Fig, 1. Calculated charge on oxygen and on proton as a function of the A1 content. (a) (b) Protonic
zeolite and zeolites exchanged with (c) Li, (d) Na, (e) K, (f) Rb, (9) Cs
specific basicities. As to the structure effect, using the Electronegativity Equalization Method
@EM) (21) which differs from the Sanderson approach (10) in that it takes into account structural
parameters, it has been shown that the ionicity of the bonds in a zeolite depends on its
crystallographic structure. Usual zeolites are ranked in the order of ionicity FAU < LTL < MFI
< MOR (21) which is different from their Sin, order ( FAU < LTL < MOR < MFI (figures 1 and
2)). This means that the ionic charge on oxygen and proton in mordenite will be increased
compared to the ones in a less ionic structure, even of similar composition. In addition and
particularly for zeolites with a low A1 content the inhomogeneity in the A1 distribution (possible
paired sites, gradient of A1 concentration ...) will also make the true charge of some specific
oxygen atoms different from the average calculated one. One may expect that the experimental
measurement of basicity will reflect these influences of the structure and of Al location.
ii) Experimental measurement of basicity
Several methods have been proposed to measure the basicity of solid materials (22,23). Some of
them have been applied to the field of zeolites. The use of Co;? as adsorbate is not well suited since
infrared studies showed that physical and chemical adsorption occur simultaneously (24) and that
various and not well defined carbonated species may be generated (25). The shift in the NH
infrared wavenumber of pyrrole adsorbed on basic zeolites may be used to evaluate the basic
strength (20). It showed that NaX are more basic than NaY (20) which is in line with figures 1,2.
Applied to various zeolite structures exchanged with alkaline cations, it is seen (Table I) that some
samples do not show any basicity like ZSM-5 for instance, even in the Cs form (12). For the
faujasite structure pyrrole adsorption detected basicity for all the X samples from LiX to CsX. In
theyseries LiY was not basic and NaY close to the limit detected. These results suggest to draw in
161
Rb Na
Cs K Li
-61
- 3.0
c
g 0.4
3
0 - - - - - -3.5
C
0
------- +
.-C
v)
a,
0.3
m
1
U
,4.5
9
4
0.2 I 1 8
0 1 2 E l ectronegativ i ty
Fig. 2. Calculated Sint and charge on oxygen as a function of cation electronegativity for usual A1
contents of zeolites (a) X, (b) Y, (c) L, (d) MOR, (e) Beta, (0 ZSM-5.
TABLE I
Shift of NH vibration of pyrrole adsorbed on zeolites and calculated average charge on oxygen
Zeolite
figures 1 and 2 the dashed lines which define the range of oxygen charges above which zeolites are
basic and below which the charge on the oxygen is not high enough to generate a significant
basicity. Such a range will be confirmed later in catalytic studies. The limit is around 3.5 for Sint
and -0.36 for the oxygen charge. It follows that none of the hydrogen form has strongly basic
oxygen. This is in general agreement with acid catalysis results. In the alkaline cation materials not
only ZSM-5 but also beta and mordenite should not show any basicity. Nevertheless pyrrole
adsorption studies could evidence an interaction of pyrrole with the basic sites of these two zeolites
(Table I). The oxygen charge in Table I is calculated for the actual composition of the materials
162
studied. It takes into account the fact that the cation exchange is not always 100 % for the major
cation. For X, Y and L zeolites the shifts of NH wavenumber upon pyrrole adsorption are in line
with the expected charge on oxygen while the NH shift obtained for mordenite and beta
demonstrate the existence of basic sites. These two zeolites are then examples of a strong influence
of the structure and/or of the Al distribution on the charge on oxygen which is not taken into
account in the Sanderson electronegativity calculation. In mordenite, cations are in location of low
symmetry and a rather large range of TOT angles exists (26). This structure induces a higher
ionicity of bonds than other structures do (21). In addition Al pairs have been proposed to exist in
niordenites (27). The existence of small bond angles, of a high bond ionicity and of Al pairs may
explain the presence of basic sites. The structure of beta zeolite has been determined (28) but little is
published for this zeolite on bond angles, bond lengths, bond ionicity and A l location. The
behaviour of beta zeolite in catalysis (29) suggests that it is less strongly acidic than its chemical
composition would suggest. Both this too weak acidity and simultaneously the present too high
basicity show a very strong influence on the framework charges of parameters related to the
structure and very likely on A1 location at this very low Al content (Al/Al+Si in the range of 0.07 to
0.09).
In the case of faujasite another probe has been also used to evaluate the basicity. Benzene just fits
the twelve ring window where it can interact weakly through the -CH with the basic framework
oxygen (30-33). I n the alkaline cation series the infrared shift of yCH and the amount adsorbed in
the 12-R window increases from the Li to the Cs form reaching a significant shift for the more
basic Cs materials (31). The LiY sample adsorbs benzene only very weakly on the oxygen showing
a weak zeolite basicity. These results are in agreement with the pyrrole adsorption results and with
the calculated results of figures 1 and 2 showing the limit basicity range. In beta zeolite a significant
interaction of benzene with the 12 R window is seen (34) which is surprising if one takes into
account only its Al content (i.e. Sinl) but which is in line with the pyrrole results.
iii) Correlations aciditv-basicitv
The opposite change in the charge of proton and oxygen seen in figure 1 should also exist for the
acidic strength of metal cation versus the oxygen basicity when no protons are present. It was
shown by the interaction of pyridine with the alkaline cations acting as Lewis sites that the Lewis
acidity decreases from Li to Cs in the alkaline cation series in faujasites (12,35).
It was also shown that the acid strength for a same cation is higher in Y than X (12) which is
parallel to the change in H+ charge with the Al content. One may conclude that generally speaking
the acid strength of a metal cation should be high at low Al content, i.e. in highly siliceous zeolites
or dealuminated materials, while the framework basicity should be low. This agrees with the
existence of conjugated acid-base pairs.
At this point the advantage of considering Sin1 for predicting trends in acid-base propenies of
zeolites has to be considered. The cases of mordenite, beta and GeX clearly show that the
predictions based on chemical composition alone are not confirmed by experimental results. A
major conclusion is that a strong influence of other parameters, (structure, topology, bond ionicity,
Al distribution) becomes very important for those materials. This opens a field of research for
163
TABLE I1
K basicity of c8 aromatics and Sin1 values for zeolites selective for each isomer
Rb
Cs K Na H
X
a
--.
m
W
0 1
0
9 4.0 4.1
'int
Fig. 3. Separation coefficient between ethylbenzene and p-xylene as a fonction of the intermediate
electronegativity of beta zeolite exchanged with (o)Cs, (0) Rb, (n) K, @) Na, (A) H.
The values of Sint for beta lie in a range - 4 to 4.2 - which is usually obtained in acidic zeolites
(Figure I). As previously for pyrrole (Table I) or benzene adsorption, beta zeolite looks like much
more basic that one would expect from the Sin1 calculation. This confirms the strong influence of
the structure or/and Al location on the charges born by the atoms in this zeolite. This is also in line
with the moderate acidity of this material (29).
The second example of separation on basic zeolites is given by the changes in the separation
165
coefficient a between methyl-2 and methyl-1 naphtalenes (46). The authors observed a decrease in
the C I ~ M N I I M N coefficient as Sin, increases upon alkaline and alkaline earth ion exchange. The
curves are distinct for X and Y zeolites.
transfer from the zeolite to the Pt particles (57). Such an explanation appears to be also valid for the
alkaline earth forms (58). Figure 4 reports the change in benzene yield in n-hexane aromatization as
a function of oxygen charge and Sin1 evaluated from (57,59). The more active catalysts (Rb and Cs
-0.34 oxygen c h a r g e
Fig. 4. Benzene yield in n-hexane dehydrocyclization at 733 K (ref 59) as a function of Sinl and
oxygen charge of PtL zeolite exchanged with (0)H, ( 0 ) Li, (A) Na, 0)
K, g)Rb, (A) Cs.
forms) for the production of benzene have the lowest Sinlvalues. This reaction is monofunctionnal,
the active sites being the Pt atoms (59). The results confirm that a high zeolite basicity increases the
aromatization activity of the Pt sites. The change in the electronic state of Pt was also shown from a
decrease in the amount of CO adsorbed on Pt and in the benzene hydrogenation activity in L
materials (58). In a series of Pt faujasites of the X or Y type exchanged with H, Na or Cs cations,
the wavenumber of CO adsorbed on Pt particles decreases simultaneously with the benzene
hydrogenation activity from the acidic to basic zeolites in the order PtHY > PtHNaY > PtNaY >
PtNaX > PtCsX (44a,60,61). Simultaneously the apparent activation energy increases from 48 to
120 KJ.mole-1 which precludes any explanation based on diffusion due to the steric hindrance of
the big Cs ions. The results show that the intrinsic electronic properties of the platinum are
gradually changed following the decrease in acidity and increase in basicity of the zeolite.
Figure 5 gives a scheme summarizing the continuous changes in properties from the strongly
acidic to the highly basic zeolites. Choosing the right Al content and the right cation is a way to
adjust for a given zeolite the properties to the expected behaviour of the solid in adsorption or in
catalysis.
Resistance to sulfur
The experimental results presented here indicate that the zeolite basicity may direct the properties
of supported metal . Changes i n the metal particles properties may be induced not only by the
167
zeolite but also by the species adsorbed on the metal. For instance sulfur atoms formed by
decomposition of sulfur compounds are electronegative and favor an electron transfer from the Pt
particles to the sulfur (62). In the case of Pt supported on acidic zeolites, the Pt-S bond is loose
since less electrons are available in the metal due to the Pt-acid interaction (62). One may expect that
acidity basic i ty
4 strength
increase increase
-
4
increase
1 benzene
increase decrease
hydrogenation
4 e N-hexane
decrease increase a r o m a t i za t ion
4
increase decrease
* resistance t o S
on the opposite, due to the electron transfer from the basic zeolites to the Pt particles, more
electrons are available in the metal to form a strong bond Pt-S. Sulfur should be a stronger poison
for m a s i c zeolites than for Pdacidic zeolites. This is in fact observed, the PtKL or PtBaL zeolites
active in the n-hexane dehydrocyclization are very sensitive to sulfur (63).
CONCLUSION
The basicity of zeolites, like acidity, varies i n a large range from weak to strong. Several
parameters which direct this basicity have teen identified. They give trends and guide lines for the
increase in basicity. The easiest of these parameters to act on are the A1 content and the
electronegativity of the cation. For instance in the case of zeolites like mordenite or beta which
show some basicity despite their low Al level, an increase in the A1 content should give a stronger
basicity. In the search of new selectivities in adsorption and catalysis, the basic zeolites offer a large
range of opportunities.
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New York, 1984.
38 Maomi Seko, Oil and Gas J., July 2 (1979) 81.
39 L.O. Stine, D.B. Broughton, (1969), US 3.636.121. to UOP ; R. Baerden Jr, R.J. De Foe,
1972, U.S. 3.686.343, to Esso.
40 a) R.W. Neuzil, (1982), U.S. 4.326.092, to UOP
b) D. Barthomeuf, (1986), U.S. 4.593.150 to Exxon.
41 a) R.W. Neuzil, D.H. Rosback, (1976), U.S. 3.943.182 to UOP
169
SUMMARY
INTRODUCTION
Modern fluid catalytic cracking (FCC) catalysts
represent a highly sophisticated class of materials. In
principle, they consist of approximately 15 to 35 wt-% of an
active zeolite component in an amorphous or clay matrix with a
minor amount of an oxide binder. Yet, on a microscopic scale
the composition of the 60 to 9 0 micron size microspheres is
considerably more complex: many different forms of zeolite Y, a
172
EXPERIMENTAL
The experimental catalysts used in this study were
commercial FCC microspheres with a clay based matrix which were
combined with surface area-stabilized silicas doped with metal
oxides to generate model matrix compounds with different intrinsic
acidities. We used an Engelhard rare earth exchanged US-Y
catalyst as the base case. The weakly acidic matrix material was
prepared by using a commercially availbale silica support modified
by a metal oxide. The moderatly acidic model matrix was based on
the same,silica modified with a group IIA metal oxide. The
strongly acidic matrix was generated by leaching aluminosilicate
clay microspheres. In some experiments, aluminum oxide was
deposited on the above silica to simulate a strongly acidic matrix
with variable site density.
The zeolitic FCC particles were steam deactivated
separately to simulate typical FCC equilibrium catalysts for 4
hours in 100% steam at 788 OC. The model matrix components were
either steamed at 732 OC for 8 hours in one atmosphere steam or
calcined at 580 OC to provide the target acid strength.
The catalysts' activity and selectivity patterns were
then determined in a modified MAT unit (modified ASTM D-3907
test). Figure 1 shows a schematic process flow diagramm of the
MAT test modified by Engelhard [9]. Figure 2 shows the catalyst
bed arrangement for the two different types of experiments. In
the "Catalyst on Top1@configuration, 3 g FCC catalyst were loaded
into the reactor tube on top of 3 g appropriately sized matrix
component. Because the reactor was of the down-flow type, the
zeolite-containing FCC catalyst was contacted by the feed first.
In the "Matrix on Top" configuration, the loading order was
inverted and the matrix component was added on top of the FCC
catalyst'bed. 1.2 g of a Mid Continent gas oil were fed in 48 s
(catalyst-to-oil ratio of 5 ) at 490 OC. The liquid product
syncrude was analyzed by GC simulated distillation (ASTM D-2887),
the gas fraction was analyzed by GC, and the coke on catalyst was
determined by a LECO coke analyzer. Activity is defined as weight
percent of gas oil converted to products boiling below 216 OC and
coke, or as a dimensionless activity based on second order
kinetics, where Activity = Conversion/(lOO - Conversion).
w
CHROYATOORAPHK:
DELIVERV ZONE 'ROGEN
I
IL W l V E R V TUBE
CALIBRATION
GAS INLET
GAS COLLECTION
CATALYST BED
RESERVOIR
GLASS REACTOR
ZONE FURNACE
MEAT
0 % COOUNT
c
r.
9
ri
ID
..
W and Zeolite Increases Cracking Activity
MAT A c t i v i t y
2.5 -
I
2-
I
1.5 ~~
1-
0.5 -
0-
Matrix Zeolite Calculated Measured
Catalyst In MAT .Test
Activity = Conv./(lOO-Conv.)
J
9
Conversion to Prod. < 216 C
177
TABLES
80
70
60
50
40
30
20
10
0
Conv. Activ. Gasol. Bottms Coke Dry Gas
Catalyst A B C
CONCLUSIONS
Our experiments using REY and RE-USY catalysts with a
minimal matrix activity in combination with model matrix compounds
of increasing intrinsic acid strength have clearly demonstrated
the following principles:
- A strong synergism exists between matrix and
zeolite cracking under FCC conditions. The resulting
activity is higher than the sum of the individual
contributions.
- It is imperative that the larger feedstock
molecules contact the matrix component first t o convert
them to smaller fragments which can be cracked inside
the zeolite to gasoline products.
- Matrix activity is a combination of acid site
strength and density. A moderately active matrix
results in a properly balanced FCC catalyst with optimal
gasoline and coke selectivities.
ACKNOWLEDGMENTS
We acknowledge the expert technical assistance of Mr.
Egberto Villanueva in preparing the Samples for this study. We
are indebted to Engelhard's Petroleum Catalyst hraluation group
for the many experiments, in particular those of the staged
bed configurations. Engelhard's Research Services group provided
the physical and chemical characterization of the samples. We
also thank S.H. Brown, M. Deeba, G.S. Koermer, J.B. McLean, E.L.
Moorehead, and D. Stockwell for many stimulating discussions.
REFERENCES
1. J. Scherzer, Catal.Rev.-Sci.Eng. , 31(3) , 215-354 (1989).
2. P.B. Venuto and E.T. Habib, IIFluid Catalytic Cracking with
Zeolite Catalystsl8, Marcel Dekker, New York (1979).
3. B.W. Wojciechowski and A . ?orma, IICatalytic Cracking
Catalysts, Chemistry and Kinetics", Marcel Dekker,
New York (1986).
4. Reference [l] above, and references therein.
5. A.G. Oblad, Oil and Gas Journal, March 27, 84 (1972).
183
' M a r t i n - L u t h e r - U n i v e r s i t y H a l l e - W i t t e n b e rg,
Department o f C h e m i s t r y , S c h l o R b e r g 2, H a l l e 4020, BRD
SUvlMARY
The s u b j e c t o f t h i s p a p e r i s t h e s y n t h e s i s o f p e n t a s i l - t y p e
INTRODUCTION
S i n c e 1966 t h e Chemie-AG B i t t e r f e l d - W o l f e n has been t h e
o n l y p r o d u c e r o f m o l e c u l a r s i e v e s i n t h e GDR. The development
s t a r t e d w i t h t h e s y n t h e s i s o f z e o l i t e 4A i n 1960. The r a n g e o f
t y p e s o f m o l e c u l a r sieve, w h i c h a r e produced f u r t h e r i n c l u d e s
t h e z e o l i t e s 3A and 5A, t h e f a u j a s i t e s 13X, 1OX and Y, morde-
n i t e and e r i o n i t e t y p e s and c u r r e n t l y a l s o t h e p e n t a s i l t y p e
Zeosorb HS 30 ( T a b l e 1). The z e o l i t e s a r e used i n v a r i o u s
a d s o r p t i v e and ca t al,,t i c processes.
The range o f p e n t a s i l t y p e b y m o l e c u l a r s i e v e s was w i d e n e d
b y u s i n g a s p e c i a l method. F o r a l o n g time the synthesis of
t h e s e t y p e s was c o n n e c t e d w i t h t h e a p p l i c a t i o n o f s u b s t a n c e s
deternining the structure, t h e s o - c a l l e d t e m p l a t e compounds,
as d e s c r i b e d i n r e f s . 1-3.
TABLE 1
Chemie-AG B i t t e r f e l d - W o l f e n as a m o l e c u l a r s i e v e p r o d u c e r
TYP e
A Fauj a s i t e E r i o n it e Mo r d e n i t e Pent a s i l
~~~~ ~~ ~ ~
The f i r s t work on t h e a p p l i c a t i o n o f o r g a n i c s u b s t a n c e s i n t h e
p r o c e s s of z e o l i t e f o r m a t i o n was c a r r i e d o u t b y BARRER and
DENNY ( r e f . 4) and KERR ( r e f . 5). T a b l e 2 shows a l i s t o f
v a r i o u s o r g a n i c compounds, w i t h w h i c h p e n t e s i l z e o l i t e s c o u l d be
pr oduc ed i n t h e y e a r s a f t e r 1966. We have grouped t h e s u b s t a n c e s
i n t o categories, such as o r g a n i c c a t i o n s , o r g a n i c a n i o n s and
n e u t r a l molecules, and h b v e l i s t e d t h e names o f t h e a u t h o r s and
the year o f publication, when t h e s e f a c t s w ere known. Important
s t a g e s a r e t h e w o rk s o f ARGAUER and LANDOLT ( r e f . RUBIN
l),
e t el. (ref. 2), KERR ( r e f . 5) and LOWE and AROYA ( r e f . 6).
From t h i s v a r i e t y and g r o u p s o f s u b s tances, the r o l e o f template
compounds i n t h e s y n t h e s i s p r o c e s s c a n be deduced t o b e u n c l e a r
and d i v e r s e ,
The a p p l i c a t i o n o f o r g a n i c compounds i n a process, w h i c h i s
otherwise e n t i r e l y inorganic, ceuses some p r o b l e m s f o r t h e
process i t s e l f , a s w e l l a s f o r t h e economy and t h e q u a l i t y o f
t h e products.
Such pr oble m s a r e , f o r instance:
- the cost o f t h e template;
- t h e p o l l u t i o n o f w e s te w a t e r ;
- s a f e t y problems i n t h e t e c h n i c a l process;
- t h e p o l l u t i o n o f t h e o r g a n i c component b y w aste gas d u r i n g
thermal decomposition;
- t h e c ar bon d e p o s i t s i n t h e z e o l i t e caused b y a p o s s i b l e
i n c o m p l e t e c o mb u s ti o n o f t h e o r g a n i c component.
These d i s a d v a n t a g e s demand t e m p l a t e - f r e e s y n t h e s i s . There-
fore, b e f o r e commencing r e s e a r c h and development w ork on t h e
synthesis of pentesil zeolites, i t was n e c e s s a r y f o r Chemie-AG
Bitterfeld-Wolfen ( a s a p r o d u c e r o f m o l e c u l a r s i e v e s ) and t h e
Research I n s t i t u t e a t H a l l e t o c o n s i d e r t h e b a s i c raw m a t e r i a l s
and t h e t e c h n i c a l f a c i l i t i e s w h i c h were a v a i l a b l e , i n o r d e r t o
make i n d u s t r i a l p r o d u c t i o n f e a s i b l e .
187
TABLE 2
The d i f f e r e n t t y p e s o f o r g n n i c compounds, w h i c h c a n be used
f o r t h e syntheses o f P e n t e s i l z e o l i t e s
TABLE 3
S y n t h e s i s o f P ,n ta s i l zeolites with different additions at
175 OC and r e s t e d r e a c t i o n m i x t u r e s
From t h e s e t e s t s , t h e f i r s t p a t e n t a b l e r e s u l t s were o b t a i n e d ,
and t h e s e a r e l i s t e d i n T a b l e 4.
C a t i o n i c and/or a n i o n i c p o l y m e r compounds a s w e l l as a t e c h n i c a l
m i x t u r e o f amines a r e u s e d as t e m p l a t e s ( r e f s . 13-14). The f i r s t
template-free synthesis w i t h o r without the eddition o f n u c l e i
o f c r y s t e l l i z a t i o n are described i n refs. 15-17.
F i g u r e 1 shows a f i e l d o f s y n t h e s i s f o r t h e t e m p l a t e - f r e e type.
The phases w h i c h c a n be seen a r e shown b y p l o t t i n g t h e r e a c t i o n
t i m e a g a i n s t v a r i a t i o n s o f t h e SiOdA1203 molar r e t i o i n t h e
reaction mixture. I n a d d i t i o n t o t h e t a r g e t phase, pentasil
w i t h a M F I - s t r u c t u r e , m o r d e n i t e , q u a r t z and l a y e r s i l i c a t e s
can a l s o be seen. Each t i m e t h e S i O d A 1 2 0 3 m o l a r r a t i o was
i n c r e a s e d a d i f f e r e n t sequence o f phases c o u l d be seen.
A t a S i02/ A1 2 0 3 m o l a r r a t i o o f 20 - 25 c o n v e r s i o n f r o m t h e
amorphous phase i n t o m o r d e n i t e o c c u r s , a t a medium m o l a r r e t i o
o f 25 - 55 c o n v e r s i o n f r o m t h e amorphous phase i n t o q u a r t z v i a
P e n t a s i l oc c u rs , e t an even h i g h e r r a t i o c o n v e r s i o n f r o m t h e
amorphous phase i n t o q u a r t z v i a l a y e r - s i l i c e t e occurs.
189
TABLE 4
E a r l i e r p a t e n t s f o r P e n t a s i l s y n t h e s i s (1982) of Chemie-AG
B i t t e r f eld- W o l f en
Number o f t h e p a t e n t Content
I
300
I
~
7004
I
,
I
24
HS 20
k-i,f---/Yfj
/
48
I
72
'
BS YO
I
96
4.-""
r r n d r n o r ~
mordenih
I
720
Y I
14.0 h
tU
ss
MF I
MOR
c---------r c---------r
5 um 2 um
/ /
F i g . 2. A r a s t e r e l e c t r o n microscope image o f t h e phases
observed i n t h e t e m p l a t e - f r e e s y n t h e s i s f i e l d .
MFI: P e n t a s i l t y p e z e o l i t e s f
SS : s h e e t s i l i c a t e e ;
MOR: M o r d e n i t e s .
191
Based on t h i s s t u d y o f t h e l i m i t a t i o n s o f t h e f i e l d o f
s y n t h e s i s end t h e k i n e t i c s o f t h e c r y s t a l l i z a t i o n process,
an e n t i r e l y i n o r g a n i c , t e c h n i c a l p r o c e s s was developed.
I n F i g u r e 3 a scheme o f t h e c o u r s e o f t h e r e a c t i o n i s gi ven.
Based on a sodium a l u m i n a t e s o l u t i o n as a s o u r c e o f A1203,
a NaOH s o l u t i o n and water, an a l k a l i n e p r e p a r a t i o n i s p r o d u c e d
i n a f i r s t m i x i n g p ro c e s s . S i l i c a s o l used as a s o u r c e of S i 0 2 ,
i s added i n a subsequent m i x i n g p ro c ess. A f t e r homogenizing,
t h e r e a c t i o n m i x t u r e i s t r a n s f e r r e d t o an a u t o c l a v e end
c r y s t a l l i z e d under hydrothermal conditions. After the reaction
has ended and h a s been c o o l e d down, t h e p r o d u c t is s e p a r a t e d
fro m t h e m o t h e r l i q u o r b y f i l t r a t i o n . I t i s t h e n washed u n t i l
t h e o u t - f l o w i n g w a t e r has a pH v a l u e o f a p p r o x i m a t e l y 9 and
d r i e d a t e t e m p e r a t u r e o f 110 OC. The p r o d u c t - Zeosorb HS 3 0 -
i s a d r i e d powder o f sodium form. T h i s i s i t e c o m m e r c i a l form.
I f r e q u i r e d , HS 3 0 - p r o d u c t s c a n a l s o be s u p p l i e d i on-exchanged
( l o a d e d w i t h d i f f e r e n t c a t i o n s ) o r g r a n u l a t e d (bound w i t h c l a y ) .
192
MIXING lstep 1
MlXING 2 step I
L DRYING (770°C) I
I
0 o wder
F i g . 3. M a n u f a c t u r i n g p r o c e s s o f t e m p l a t e - f r e e Pentasil
type zeolite.
When c om pa ri n g t h e p r o p e r t i e s o f t e m p l a t e - c o n t a i n i n g and
template-f ree synthesized products, according t o t h e i r S i O d
A1203 ratio, i t can be f o u n d t h a t t h e i r c r y s t a l l i n i t y , S i O d
A1203 ratio, mo rp h o l o g y and a c i d i t y cnn be v a r i e d s y s t e m a t i -
c a l l y i n t h e t e m p l a t e - f r e e v a r i s n t as w e l l , although t h i s i s
o n l y p o s s i b l e w i t h i n a s m a l l range. I n t h i s respect, there
a r e s i m i l a r and d i f f e r e n t t e n d e n c i e s . These a r e g i v e n i n
T a b l e 5.
TABLE 5
Comparison o f t h e p r o p e r t i e s o f t e m p l a t e - c o n t a i n i n g and t e m p l a t e -
f r e e P e n t a s i l p r o d u c t s ( g e n e r a l t e n d e n c i e s depending on t h e
Si0,./A1203 ratio
S i m i l a r tendencies D i f f e r e n t tendencies
1. C r y s t a l l i n i t y 1. dep e n d e n c y o f t h e v o l u m e
o f t h e u n i t c e l l upon t h e
2. volume o f m i c r o p o r e s SiOgAl2O3 r a t i o
3. r e l a t i o n between t h e 2. r a t i o o f weak a n d s t r o n g
Si02/A1 0 r e t i o s o f a c i d i c centres
the reaztlon mixtures
a nd t h e p r o d u c t s 3. volume o f mesopores
4. dependence o f t h e
m o r p h o l o g y upon t h e
Si02/A1203 r a t i o
5. d i r e c t r e l a t i o n between
t h e A1 c o n t e n t and t h e
Broensted-acidity
F o r example, t a b l e 6 shows a c o m p a r i s o n o f c h a r a c t e r i s t i c d a t a
o f s e l e c t e d samples f r o m b o t h s e r i e s , e i t h e r with template
- letter S - o r without template - l e t t e r A. With an i n c r e a s i n g
Si02/A1203 r a t i o , the acidity, which i s given here as t h e
a d s o r b e d q u a n t i t y o f NH3, decreases i n b o t h s e r i e s . Th e v o l u m e
of t h e micropores, d e t e r m i n e d f rom n-Hexane adsorption isotherms,
is, w i t h an e q u a l volume, independent o f t h e SiOdA1203 m o l a r
r a t i o i n both series.
T h e vo lume o f t h e mesopores o f t h e s a m p l e s s y n t h e s i z e d w i t h
TPA-J i s t w o o r t h r e e t i m e s l a r g e r i n c o m p a r i s o n t o t h e
template-f ree v a r i a n t .
By c o m p a r i n g t h e m o r p h o l o g y o f t h e p r o d u c t s o f b o t h t h e
series (Figure 4), i t i s p o s s i b l e t o see t h a t w i t h an i n c r e a s i n g
SiO/A1203 m o l a r r a t i o t h e r e i s a l w a y s a change f r o m l o o s e
a g g r e g a t e s t o l a r g e r m o n o c r y s t a l s w i t h a smooth su-face.
A l t h o u g h t h e r e i s no d e t a i l l e d i d e n t i t y b e c a u s e t h e f o r m a t i o n
o f a s p e c i a l m o r p h o l o g y depends o n t o o many f a c t o r s , the
t e n d e n c y i s t h e same.
194
TABLE 6
Comparison o f p r o d u c t p r o p e r t i e s a c c o r d i n g t o t h e i r s y n t h e s i s
w i t h ( S ) and w i t h o u t ( A ) t e m p l a t e s (H-forms) SiOdA1203 r a t i o
1. By u s i n g s y n t h e s i s v a r i a n t s f o r w i d e n i n g t h e r a n g e o f t h e
S i 0 2/ A1 203-m o d u 1e .
2. V a r i n g t h e p r o p e r t i e s b y isomorphous s u b s t i t u t i o n o f t h e
n e t w o rk-f o r m i n g e l e m e n t s .
3. I n c r e a s i n g t h e module b y subsequent d e a l u m i n i z a t i o n .
By u s i n g s p e c i a l v a r i a t i o n s o f t h e s y n t h e s i s c o n d i t i o n s
(concentration o f a l k a l i metals, c r y s t a l l i z e t i o n time) , i t i s
p o s s i b l e t o extend t h e renge o f t h e module o f t h e s y n t h e s i z e d
p r o d u c t s t o 20 - 60 f r o m a s t a r t i n g m o l a r r a t i o o f 20 - 70.
K i t h an i n c r e a s i n g m o l a r r a t i o , the rate of crystallization
decreases. With a s t c r t i n g m o l a r r a t i o o f 80 -
100 t h e r e p r o d u c i -
b i l i t y is p o o r , a n d t h e r e w i l l b e a d e c r e a s e i n t h e c r y s t a l l i n i t y
of t h e products.
196
D t
I r o
@ O D
w m
a m
L
a
I-
y.
I
O N
e,m W
m C
4 0)
0 L
E O
W N
r N
..
Q)c
me,
mrl
E l
rl
0
a,@
P N
0.4
0 0
ma,
Or:
Le,
v c
4%
€ 0
196
The r e s u l t s of t h e s y n t h e s e s w i t h b o r o n a r e shown i n F i g u r e 5.
The r e s u l t a n t r e l a t i v e c r y s t a l l i n i t y (compared t o a s t e n d a r d )
o f synthesized products obtained a f t e r a c r y s t o l l i z a t i o n time
( T K ) o f 24 o r 4 8 h o u rs , and a t a t e m p e r n t u r e o f 175 OC (TK),
depending on t h e S i 0 2 / A 1 2 0 3 m o l a r r a t i o i n t h e r e a c t i o n m i x t u r e ,
a r e shown. On t h e b a s i s o f a s t a n d e r d Si02/A1203 i n i t i a l r a t i o
o f 40, alum ini u m was c o n s t a n t l y r e p l a c e d t o a c e r t a i n p e r c e n t a g e
by B ( u p p e r l i n e o f F i g u r e 4), w h i a l e t h e r a t i o o f S i O d A 1 2 0 3 +
+B203 remained c o n s t a n t a t 40. Up t o a s u b s t i t u t i o n o f a p p r o x i -
m a t e l y 50% A l , w e l l - c r y s t a l l i z e d p r o d u c t s a r e o b t a i n e d . W i t h
l a r g e r boron content, the c r y s t a l l i z a t i o n of p e n t s a i l i s
suppressed. T h i s can be e x p r e s s e d b y t h e g r e a t d r e c r e a s e i n
crystallinity. A p a r t fro m M F I - t y p e z e o l i t e , amorphous phases
and l a y e r - s i l i c a t e s a r e s t i l l found, and t h e r e a r e a l r e a d y
t r a c e s o f more h i g h l y - c o n d e n s e d S I O -phases, such as c r i s t o b a l i t e .
2
197
%&\ '
55 - sheet silicates
Cr - cristoba/i te
am - amorphous
I I I
50 700 750 21
product 5102/Ab 0
' -ratio
F i g . 5. S y n t h e s i s o f P e n t a s i l t y p e z e o l i t e s w i t h b o r o n
s t a r t i n g Si02/A1203 + B 2 0 3 - r a t i o = 40 TK = 175 OC
H-HS
H-HS
30
30
-
thermal
-1073
6 n HC1
EOTA, i n tic1
29.6
32.4
64.0
58.8
66.3
12.0
54.1
11.5
-
5.2
H-HS 30 thermal 1073 NH OH, i n HC1 31.4 60.6 12.0 12.7 3.4
H-HS 30 thermal 1073 6 8HC1 32.5 58.6 12.0 11.6 5.4
H-HS 30 hydro- 623 6 n HC1 313.5 49.9 30.7 32.3 14.1
the rmel
H-HS 30 hydro- 773 6 n HC1 55.7 34.9 15.1 14.2 29.1
t hermel
H-HS 30 hydro-
thermal
973 6 n HC1 71.8 27.3 2.4 - 36.7
remove A 1 f r om t h e l a t t i c e i n o r d e r t o a c h i e v e t h e r e q u i r e d
a c i d i t y . We t e s t e d Zeosorb HS 30 as a b a s i c m a t e r i a l i n t h e r m a l
and h y d r o t h e r m a l t r e a t m e n t processes. These p r o c e s s e s can b e
f o l l o w e d b y e x t r a c t i o n s t e p s f o r t h e d i s p o s a l o f t h e removed
alum inium ( t h e e x t r a - l a t t i c e a l u m i n i u m ).
The e f f e c t s t h a t can b e a c h i e v e d a r e shown i n f a b l e 7.
Th er m al t r e a t m e n t was c a r r i e d o u t a t t e m p e r a t u r e 8 f r o m 500 OC
t o 1000 OC i n a f l a t - b e d f o r a p e r i o d o f 0,5 t o 24 h. I n Table 8
some examples a r e g i v e n . 0 y c h o o s i n g t h e t e m p e r a t u r e and/or
p e r i o d o f treatment, t h e c o n t e n t o f A1 i n t h e l a t t i c e can b e
varied systematically.
TABLE 8
P e n t a s i l t y p e z e o l i t e Zeosorb HS 30 f i e l d s o f a p p l i c a t i o n i n
t h e GDR
-- cc aa tt aa ll yy ss tt for
for
a h y d r o - c r a c k - f o r m i n g p r o c e s s (Leuna)
a dewaxing p r o c e s s (Schwedt, BBhlen)
-- cc aa tt aa ll yy ss tt for
for
h y d r o r a f f i n a t i o n (Schwedt)
h y d r o t r e a t i n g (Schwedt)
However, i t i s i m p o s s i b l e t o re d u ce t h e t o t a l c o n t e n t o f A1
i n t h e samples, even u n d e r d r a s t i c e x t r a c t i o n c o n d i t i o n s . The
s p e c i e s o f A 1 o b t a i n e d b y t h e r m a l t r e a t m e n t remai n i n t h e
sample as e x t r a - l a t t i c e aluminium.
H y d r o t h e r m a l t r e a t m e n t makes a s p e c i f i c a d j u s t m e n t o f t h e
content o f A1 i n the l a t t i c e possible, end, apart from t h 3 t ,
t h e p c r t i o l e x t r a c t i o n o f t h e removed a l u m i n i u m ( u p t o 60%) from
t h e l a t t i c e system o f t h e z e o l i t e . T h i s i s i m p o r t a n t f o r t h e i r
a p p l i c a b i l i t y as c a t a l y s t o r c a t s l y s t c a r r i e r s . Comparing t h e
e f f i c i e n c y o f b o t h processes o f after-treatment, we f i n d t h a t :
- with b o t h p r o c e s s e s p r o d u c t s cen b e manufactured, that other-
w i s e can o n l y be s y n t h e s i z e d w i t h t h e h e l p o f t e m p l a t e s ,
- d u r i n g hydrothermal treatment the tempersture o f adjustment
f o r a c e r t a i n c o n t e n t o f A 1 i n t h e l a t t i c e can be
150 O C t o 200 OC l o w e r,
- i n comparison w i t h t h a t , l e s s equipment i s needed f o r t h e
thermal treatment.
A? P L I
CAT I
ONS
F o r s p p l i c a t i o n as c e t o l y s t c a r r i e r s , i o n exchange w i l l be
n e c e s s a r y i n most cases. F o r r e a c t i o n s u s i n g an a c i d i c c a t e l y s t
t h e H-form i s s u i t a b l e i n most coses. I t can be a c h i e v e d b y
+
!JH4 - i o n e x c h a n g e o r by t h e d i r e c t a c t i o n o f a c i d s , as Zeosorb
HS 30 i s s t a b l e t o a c i d s . F o r s p e c i a l p r o c e s s e s a m o d i f i c a t i o n
w i t h v a r i o u s m e t a l c a t i o n s w i l l be necessary. A modification
o f HS 30 w i t h Zn2+- o r K + - i o n s p r o v e d t o be s u i t a b l e f o r o b t a i n -
i n g a r o m a t i c s by p e t r o c h e m i c a l p r o c e s s e s . The c a t a l y t i c e x p e r i -
ments were c a r r i e d o u t a t t h e C e n t r a l I n s t i t u t e of O r g a n i c
C h e m i s t r y ( Z e n t r a l i n s t i t u t f u r O r g e n i s c h e Chemie) at Leipzig
under t h e supervision o f Prof. Anders.
O t h e r a p p l i c c t i o n s o f Z e o s o r b I-IS 30 i n i n d u s t r i z l ~ r c c t ? . " E i
in t i l e ?'X :,r? choi!ii i n T a b l e 8.
201
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This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 203
0 1991 Elsevier Science Publishers B.V.,Amsterdam
SUMMARY
A s e r i e s o f s t u d i e s were made on the use o f z e o l i t e c a t a l y s t s f o r producing
selectively some s p e c i f i e d hydrocarbons from synthesis gas. They are
e x e m p l i f i e d by t h e s e l e c t i v e production o f gasoline, r i c h i n i s o p a r a f f i n s , by
Ru-Pt b i m e t a l l i c c l u s t e r supported on protonated Y z e o l i t e and t h a t of C3 and
C4 p a r a f f i n s , s u b s t i t u t e s f o r LPG, by use o f a h y b r i d c a t a l y s t comprising Y-
type z e o l i t e and methanol synthesis c a t a l y s t , etc. For e l u c i d a t i n g t h e
s p e c i f i c product s e l e c t i v i t y , r e a c t i o n mechanisms are discussed i n terms o f t h e
balance and p r o x i m i t y o f the r e l e v a n t d i f f e r e n t k i n d s o f a c t i v e s i t e s f o r
consecutive reactions.
INTRODUCTION
Fischer-Tropsch process i s i n i n d u s t r i a l o p e r a t i o n a t SASOL producing m o s t l y
aliphatic 1i q u i d hydrocarbons from synthesis gas. I t gives, however,
quantities of methane and o t h e r gaseous hydrocarbons as byproducts. In the
f i x e d bed reactor, operated a t lower temperature, a l a r g e amount o f medium wax
is a l s o produced. A d d i t i o n a l l y , non-hydrocarbon c o n s t i t u e n t s such as alcohol,
aldehyde and a c i d are found i n t h e l i q u i d product. Obviously t h e r e exists a
strong need t o improve the process f o r b e t t e r y i e l d and q u a l i t y o f t h e liquid
fuels.
In t h i s connection, carbon number d i s t r i b u t i o n s o f F-T synthesis products
over b u l k c a t a l y s t s , such as p r e c i p i t a t e d o r fused i r o n employed a t SASOL, are
g e n e r a l l y found t o f o l l o w "Schulz-Flory-Anderson (SFA) Law" ( r e f . 1). Provided
t h e l a w works, t h e l a r g e s t y i e l d o f gasoline, C5 t o Cll, can n o t exceed 48% by
weight a t a chain growth p r o b a b i l i t y f a c t o r a = 0.7 - 0.8.
Non-Schulz-Flory-Anderson k i n e t i c s , however, has been r e p o r t e d f o r zeolite
encapsulated Ru ( r e f . 2 ) and Fe ( r e f . 3) c a t a l y s t s , over which g a s o l i n e yield
was significantly improved. The use o f z e o l i t e as support f o r F-T synthesis
offers another advantage over t h e conventional b u l k catalysts: namely the
formation of branched-chain p a r a f f i n s ( r e f . 4) p o s s i b l y due to bifunctional
characteristics of t h e z e o l i t e supported c a t a l y s t . Isomerization of light
p a r a f f i n s f o r octane number improvement i s commercially c a r r i e d o u t on various
bifunctional catalysts consisting of noble metals such as Pt on acidic
supports i n c l u d i n g z e o l i t e .
204
TABLE 1
S y n t h e s i s gas c o n v e r s i o n over HY z e o l i t e - s u p p o r t e d Ru-Pt c a t a l y s t a .
~~
CO c o n v e r s i o n S e l e c t i v i t y (wtW)
Cata 1ys t (XI Carbon number i/n ratio
‘1 ‘4 ‘5’ ‘4 ‘5 ‘6-‘10
HYER 6.5 6.5 24 66 6.8 30 11
HY2R2P 13 7.0 22 66 10 40 16
( HYZR+HYZP ) b 6.1 7.8 31 56 6.5 24 7.6
HYO. 5R2P 1.5 41 17 33 7.5 12 4.8
HY 1R2P 3.6 13 31 31 9.3 27 6.5
HY4R2P a5 90 1.6 5.2 0.2 4.4 3.0
HY8R2P 19 16 18 56 0.3 1.7 1.0
aReaction c o n d i t i o n s : 240OC. 1.5 MPa, W/F = 7.0 g-cat. h/mol, CO/Hz = 2/3,
a f t e r 5 h on stream.
bW/F = 14.0 g-cat. h/mol.
HYlR2P
0 HY2R2P
A HY4R2P
Carbon number
TABLE 2
Dispersion o f metal p a r t i c l e s and t u r n o v e r number
aRefer t o t h e d e f i n i t i o n i n Ref. 6.
bVolume-area mean diameter determined by TEM.
CTurnover number f o r CO conversion a t 24D°C, 1.5 MPa and W/F = 12.5 g-cat.
h/mol.
Characterization o f catalysts
I n t h e p r e p a r a t i o n o f b i m e t a l l i c c a t a l y s t s , t h e main problem i s whether b o t h
elements are a l l o y e d o r not. The XRD p a t t e r n o f HY2R2P showed t h e presence o f
a broad diffraction band centered a t 28 = 40.7', characteristic of Ru-Pt
alloys. There was no XRD evidence o f a monometallic Ru or P t phase i n HY2R2P.
TEM observations showed t h a t the HYZR c a t a l y s t has a narrow particle size
distribution with a maximum f r a c t i o n below 10 A. Hence t h e metal particles
seem t o e x i s t i n supercages. On t h e o t h e r hand, HY2R2P and HY2P e x h i b i t e d wide
distributions: t h e mean m e t a l l i c p a r t i c l e s i z e s were 28 and 35 A, respectively.
The results o f H2 and CO chemisorption a r e given i n Table 2, which also
shows the d i s p e r s i o n o f metal (D) c a l c u l a t e d on t h e b a s i s of TEM, assuming
cubic metal c r y s t a l l i t e s . There seems t o be s a t i s f a c t o r y agreement between t h e
D values from TEM and H/M, suggesting t h a t t h e adsorption s t o i c h i o m e t r y can be
reasonably assumed t o be u n i t y f o r b o t h Ru and P t .
The turnover number f o r CO conversion, Nco, was c a l c u l a t e d on t h e b a s i s of
H2 chemisorption and t h e r e s u l t s a r e given i n Table 2. A comparison of the
turnover number of HY2R2P w i t h t h a t o f HYPR i s not straightforward, as a
considerable amount of hydrogen i s adsorbed on P t , where t h e s p e c i f i c activity
i s much lower. It i s tempting t o speculate t h a t t h e t u r n o v e r number o f HY2R2P
was increased b y a l l o y i n g Ru w i t h Pt. However, one must c o n s i d e r t h e g e n e r a l l y
observed trend o f increases i n t h e t u r n o v e r number w i t h increasing particle
size (ref. 10). Attempts t o improve t h e a c t i v i t y o f HY2R by increasing the
p a r t i c l e s i z e were unsuccessful.
It should also be noted t h a t t h e a d d i t i o n of P t resulted in a drastic
decrease in t h e (CO/M)/(H/M) = CO/H r a t i o . Chen e t al. suggested that for
207
I n f l u e n c e o f alkene a d d i t i o n
Alkenes a r e p r o b a b l y t h e p r i m a r y p r o d u c t s o f F-T s y n t h e s i s o v e r t h e z e o l i t e -
supported Ru c a t a l y s t s ( r e f . 11). The p r e f e r e n t i a l f o r m a t i o n o f branched-chain
alkanes .might be due t o t h e a c i d - c a t a l y z e d i s o m e r i z a t i o n o f the alkenes on
zeolite sites, f o l l o w e d d i r e c t l y by h y d r o g e n a t i o n t h e Ru s i t e s . It can be
expected that the r e l a t i v e r a t e s o f the acid-catalyzed and metal-catalyzed
r e a c t i o n s should determine p r o d u c t s e l e c t i v i t y .
To check t h e p o s s i b i l i t y of h y d r o c r a c k i n g r e a c t i o n s c o n c u r r e n t w i t h t h e F-T
synthesis, c6-c12 1-alkenes were a l l o w e d t o r e a c t t o g e t h e r w i t h s y n t h e s i s gas
over OAHYZRZP. The carbon number d i s t r i b u t i o n s o b t a i n e d w i t h t h e a d d i t i o n of
1-hexene, 1-octene, and 1-decene were examined, By s u b t r a c t i n g the portion
i n h e r e n t i n CO hydrogenation, a c a t i o n i c c r a c k i n g p a t t e r n can be achieved. For
example, the extensive formation of C4 f r o m C8 could be attributed to
208
E f f e c t o f support
The carbon number d i s t r i b u t i o n o f the products from t h e CO-HE r e a c t i o n was
shifted t o t h e l i g h t s i d e i n t h e o r d e r : NaYZRZP ( r e f . 5) < HYZR2P < DAHYEREP
(ref. 6). When 1-octene was added t o s y n t h e s i s gas, t h e product distribution
was a f f e c t e d by concurrent c r a c k i n g o f 1-octene; w i t h apparent conversion o f 1-
octene a f t e r 2-3 h on stream i n c r e a s i n g i n t h e order: NaY2R2P (15%) < HYZREP
(26%) < OAHYZRZP (65%). As a r e s u l t , t h e y i e l d o f C3-C7 hydrocarbons increased
by 1-octene a d d i t i o n i n t h e same order: NaY2R2P < HY2RZP < DAHY2R2P.
TPD measurements o f NH3 revealed t h a t t h e amounts o f weak and s t r o n g acids,
d e f i n e d as t h e amount o f ammonia desorbed below and above 350 OC respectively,
were as follows: NaYZREP (1.51/0.20 mmol g-cat.-l), HY2REP (4.17/0.43 mmol g-
cat.-’), and DAHYEREP (3.42/0.68 mmol g-cat.-’). Therefore, the cracking
tendency o f 1-octene could be r e l a t e d t o t h e amount o f s t r o n g a c i d sites on
the catalysts: NaYZRZP < HYERZP < DAHYERZP. It is generally known that
cracking requires strong acid s i t e s (ref. 12).
Carbon number
of fed alkene 2 3 4 5 6 7 8 9 10 11
Cross chain
propagation
Catalyst preparation
Several k i n d s o f methanol s y n t h e s i s c a t a l y s t were employed. Pd/ID catalyst
(Pd 4 w t % ) was prepared by i m p r e g n a t i n g a commercially a v a i l a b l e s i l i c a g e l
( F u j i Davison ID, s p e c i f i c s u r f a c e area 270 m2 /g, mean p o r e d i a m e t e r 140 A)
w i t h p a l l a d i u m c h l o r i d e from i t s a c i d i c aqueous s o l u t i o n , f o l l o w e d by d r y up i n
an a i r oven and r e d u c t i o n i n f l o w i n g hydrogen a t 400 OC. Cu-Zn(H) catalyst(Cu
40, Zn 23. A1 27 atom %, r e s p e c t i v e l y ) was prepared in this laboratory
following the method described by Shimomura. Cu-Zn(C) catalyst was a
commercially a v a i l a b l e from BASF (S8-45).
For t h e sake o f c o n v e r t i n g methanol i n t o a r o m a t i c hydrocarbons, different
kinds of a c i d i c z e o l i t e s were employed upon m i x i n g w i t h the above methanol
synthesis catalysts. ZSM-5 was prepared a c c o r d i n g t o t h e method d e s c r i b e d in
the patent: t h e i r c r y s t a l l i t e s i z e was c o n t r o l l e d by changing t h e temperature
o f hydrothermal synthesis. H-M stands f o r Zeolon 100H m o r d e n i t e o b t a i n e d from
Norton Co. De-aluminated Y t y p e z e o l i t e , DAY, was s u p p l i e d by Shokubai Kasei
I n d u s t r i e s , Ltd.
The H y b r i d c a t a l y s t s were o b t a i n e d as f o l l o w s : Equal p o r t i o n by weight of
213
TABLE 3
Synthesis gas conversiona over h y b r i d c a t a l y s t s b : E f f e c t o f t h e
combination on product y i e l d .
Product y i e l d ( C%)
Hydrocarbons 9.6 8.0 12.6 17.0 15.9 35.7
Oxygenates tr. tr. tr. 0.6 1.5 5.3
CO2 5.4 3.3 10.0 16.2 14.7 30.7
Coke 0.6 3.1 1.9 - 0.4 -
Hydrocarbon d i s t r i b u t i o n (CW)
c1+c2 25.7 52.5 22.0 21.2 11.7 13.9
c3 33.3 24.8 41.6 26.9 17.8 24.7
c4 6.2 5.3 26.3 12.7 49.4 49.6
c5+ 4.2 6.4 10.1 35.5 21.1 11.9
Aromatics 30.6 10.6 tr. 3.8 0 tr.
M 6o
C
I I I I I I
1 2 3 4 5 6
Carbon number / -
Fig.5 Comparison o f hydrocarbon d i s t r i b u t i o n s by C number i n synthesis gas
conversion f o r lower p a r a f f i n production.
215
TABLE 4
In-pore d i f f u s i o n r a t e a o f propylene i n z e o l i t e
TABLE 5
Synthesis gas conversiona over h y b r i d c a t a l y s t Pd/ID+ZSM-5b
: Effect o f z e o l i t e c r y s t a l s i z e on product d i s t r i b u t i o n
increased i n p r o p o r t i o n t o t h e c r y s t a l l i t e size.
P r o b a b i l i t y o f hydrogenation o f t h e o l e f i n s escaped from z e o l i t e i s another
factor t o determine t h e product p r o f i l e . The r a t e depends on p r o x i m i t y o f the
a c i d s i t e s and t h e hydrogenation s i t e s , i n o t h e r words, t h e mode o f m i x i n g the
two component c a t a l y s t s . H y b r i d c a t a l y s t so f a r employed i n t h i s study is a
powdery mixture. I n comparison w i t h t h i s , g r a n u l a r m i x t u r e s a r e proposed and
tested. Two stage processing o f synthesis gas represents t h e extreme case of
separate use, where the f i r s t reactor i s loaded with methanol synthesis
catalyst, while t h e second one w i t h z e o l i t e t o which t h e e f f l u e n t s from the
f i r s t r e a c t o r are supplied w i t h o u t separation o f unconverted s y n t h e s i s gas.
The performances o f t h e r e s p e c t i v e mode o f using t h e two component c a t a l y s t s
are compared i n Fig.6, indicating t h a t the v e r s a t i l i t y o f product profile is
216
2-Stage
Granular
Mixture
Powdery
Mixture
Cata 1y s t
30
30
--n
30i JL
l
DME
Product
-
&
1
Dp:O. 8mm
D :1.7mm
n
Dp: 0.5mm
Dp :0.3mm
-riF1
D :0.8mm
P
2 3
Carbon number
4 5 6+ arom.
/ -
C nH2nt 2 -+--
"> Methyl benzenes
REFERENCES
1. M.E. Dry, " C a t a l y s i s - Science and Technology", (ed by J.R. Anderson and M.
Boudart,), Springer-Verlag, B e r l i n , Vol. 1, 1981, p.159.
2. H.H. N i j s and P.A. Jacobs, J. Catal. 65, (1980) 328-334.
3. D. B a l l i v e t - T k a t c h e n k o and I. Tkatchenko, J. Mol. Catal., 13, (1981) 1-10.
4. D.L. King, J. Catal., 51 (1978) 386-397.
5. 0. Okuda. T. Tatsumi, K. Fujimoto, and H. Tominaga, Chem. L e t t . , (1983)
1153-1 156
6. T. Tatsumi. Y.G. Shul, T. Sugiura, and H. Tominaga, Appl. Catal., 21,
(1986) 119-131
7. Y.G.
.
Shul, T. Sugiura, T. Tatsumi, and H. Tominaga, Appl. Catal.. 24,
(1986) 131-143.
8. T. Tatsumi, Y.G. Shul, Y. A r a i . and H. Tominaga, "Proc. o f 7 t h I n t e r n l .
Z e o l i t e Conference." ed. b y Y. Murakami, A. Iijima and J.W. Ward,
Kodansha- E l s e v i e r , Tokyo (1986), pp.891-898.
9. Y.G. Shul, Y. A r a i , T. Tatsumi, and H. Tominaga, B u l l . Chem. SOC. Jpn.,
60, (1987) 2335-2341 .
10. Y.W. Chen, H.Y. Wang and J.G. Goodwin, Jr., J. Catal., 83, (1983) 415-427.
11. Y.W. Chen, H.T. Wang and J.G. Goodwin, Jr., J. Catal., 85. (1984) 499-508.
12. A. Corma and B.W. Wojciechowski, Catal. Rev.-Sci. Eng., 27. (1985) 29-150.
13. C.D. Chang, W.H. Lang and A.J. S i l v e s t r i , J. Catal.. 56 (19790 268-273.
14. K. Fujimoto, Y. Kudo and H. Tominaga, Nippon Kagaku K a i s h i , (1982) 206-212.
15. H. Saima. K. F u j i m o t o and H. Tominaga, Chern. Lett., (1984) 1777-1780.
16. K. Fujimoto. Y. Kudo and H. Tominaga, J. Catal., 87 (1984) 136-143.
17. H. Saima, K. F u j i m o t o and H. Tominaga, B u l l . Chem. SOC. Jpn., 58 (1985)
795-802.
18. K. Fujimoto, H. Saima and H. Tominaga, B u l l . Chem. SOC. Jpn.. 58 (1985)
3059-3060.
19. K. Fujimoto, H. Saima and H. Tominaga, J. Catal., 94 (1985) 16-23.
20. K. Fujimoto, H. Saima and H. Tominaga, Ind. Eng. Chem. Res. 27 (1988) 920-
926.
21. K. Fujimoto, K. Asami, H. Saima, T. Shikada and H. Tominaga, Ind. Eng.
Chem. Prod. Res. Dev., 25 (1986) 262-267.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 219
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
The 129Xe-NMR of adsorbed xenon is a technique generally used at room
temperature for determining some zeolite properties, specially void spaces
(dimensions of channels or cages, structural defects...). This study indicates
more exactly what experimental conditions should be used, depending on
the nature of the sample and the property studied; namely: influence of
temperature, of Si/Al ratio of zeolite and more generally of chemical
composition of molecular sieves. Applications are related to complex
structures and intergrowth of structures.
INTRODUCI'ION
Many properties or defects of zeolites or metal-zeolites are difficult to
detect by classical physico-chemical techniques. For example: short-range
intergrowth of structure, short-range crystallinity, size of supported metal
particles too small to be detected by electron microscopy .... That is why, in
1978, Fraissard et a1 (ref. 1) started to search for a new molecular probe in
order to elucidate some zeolite properties which are normally difficult to
handle.
The central idea of this project was to find a molecule, non-reactive,
particularly sensitive to its environment, to collisions with other chemical
species and to the nature of adsorption sites, which could be used as a probe
for determining certain zeolite properties in a new way. In addition, this
probe should be detectable by NMR since this technique is particularly
suitable for investigating electron perturbations in rapidly moving
molecules.
Xenon is an ideal probe because it is an inert gas, monoatomic. with a
large spherical electron cloud. From the NMR point of view, the 129Xe isotope
has a spin of one-half. Its natural abundance in xenon is 26% and its
sensitivity of detection relative to the proton is 10-2. The high polarizability
of t h e xenon atom makes it very sensitive to its environment. Small
variations in the physical interactions with this latter cause marked
220
Dc, Ds and Dxe are the diameters of the cylinder, the sphere and the xenon
atom, respectively.
F: Ferrierite
Z-5, 48, 12: Z S M J , 48 and 12
A-5, 11, 17: A1m4-5, 1 1 and 17
S-34, 37: SAPO-34 and 37
b
0 1 2 4 6 e A i
-
Fig. 3. Variation of against the mean free path 1 .
With a more complicated structure we must feed the computer the real
structure of the zeolite considered. Then we circulate a xenon atom within
this space, assuming that the velocity vector is random and all directions are
223
-
equally probable. The mean free path, 1 , is obtained by averaging the
distances between successive collisions.
The result thus obtained for various model zeolites is shown in Fig. 3-1.
This curve has enabled us to determine the characteristics of the void
volumes of unknown structures or structural defects. But certain points have
to be considered more closely. For example, is 26OC a high enough
temperature for the rapid exchange model to be used? Up to what point is
the effect of the A1 concentration negligible? And, more generally, what is
the effect of the chemical composition of the solids, in particular of AlPO4,
SAPO, etc? It is obvious that if one increases 6 a or the probability of state A
one must in theory increase the experimental 6 value. But, as we shall see
-
later, the magnitude of this variation depends also on <tiv>, which depends
not only on 6 a but also on 1 , compared to 6a. Therefore, it is necessary to
study the influence of the different parameters aforementioned.
INFLUEiNCT OFTEMPERATURE
The chemical shift variations with xenon concentration 6 = f(n) at
different temperatures are illustrated in Figs. 4 and 5 for NaY and ZSM-5
samples, respectively, pretreated at 4OOOC and 10-4 torr.
Figure 4 can be divided into two
6 regions, I and 11, corresponding to
E the xenon concentration range of
a
at A Ocn,cl and 1<nQ<2, respectively.
When T>O"C, 6 varies linearly with
n in both regions. The slope of the
6 = f(n) variation decreases with
increasing temperature. When
T<O°C, 6 = f(n) is still linear and its
slope decreases slightly with
temperature in region I1 (line AB).
On the contrary, in region I, the
6 = f(n) variation changes from
linear to concave. More precisely,
at low n, the chemical shift value is
constant (line CD) up to a certain
value of the xenon concentration,
Fig. 4. 6=f(n) variations for Y zeolite nc. then increases with xenon
at temperatures TOC: (0) -100; (1> -80; concentration.
(0) -60; Q -40; (A) -20; (0) 0; (0) 27; In the case of ZSM-5 (see Fig. 5),
50; @) 80;e) 100. between -100 and 27°C. the
224
6s
E -
I
0.
Q
90 -
70
50 -
1
T,,,,,,,,,,,,,,
-100 0 100 TVC
where Dxe is the xenon diameter, P a and p v are the xenon density in the
adsorbed state and in the free space, respectively. A and V are the surface
area and the volume of the free space, respectively. K (K=pa/pV) is the
reduced probability ratio of xenon residences on the surface (A) and in the
free space (V). It depends upon the zeolite structure and the temperature. C
(C=V/ADxe) is a constant for a given system.
To see whether the fast site exchange model is valid, and if it is valid,
then in what temperature range, we rearrange equation (3) to:
Furt hermore :
0 l l , l , , l , l ,
A
- O\O
states A and V. It is a constant
for a given system. Therefore, if
m
Y I \ the model is valid, then the
Ln [ (6a-6s)/(6s-<6v>)]=f( I I T ) plot
“0,
2 -0.5 - -
co: \O
should be a straight line.
To get the experimental
-e
“0,
c;l Ln [ (6a-6s)/(6s-<6v>)]=f(1I T ) plot
we need to know 6aand <av>. As
\ \ Q \
obtain the experimental plot illustrated in Fig. 7. One can see that at high
temperature (T>30°C) the plot is a straight line which means the model is
valid (ref. 8).
- the rapid exchange model and, firstly, the
Let us consider then
dependence of <tiv> on 1 . When the xenon leaves the surface 6v=6a. Then, if
- -
1 is small <tiv> is hardly less than tia. On the other hand, when 1 is large the
xenon atom has time to lose the memory of the perturbation, caused by
adsorption, before the next collision with the surface. <tiv> can therefore be
very small, even zero, given that the electronic relaxation is very rapid.
When the temperature T falls, the residence time of adsorbed xenon
increases and, consequently, the probability na/na+nv of this state. The
variation of 6 then depends on <tiv>. It will be very small if <6v>-6a (ZSM-5)
or, conversely, very large if < & V > < < & a (Nay). This study of the temperature
dependence is a way of checking the size of the pores in which the xenon is
adsorbed.
Fig. 8. 6=f(n) (full lines) and line width Av=f(n) (dotted lines) variations for
ZSM-I1 with Si/Al: (0) 30; (A) 40;(0) 80; (a) 160; (+)
OQ.
221
Hot
t
115 -
115
110 -
I
I
I-/
I
change for a definite value of the
aluminium concentration [A1]=2
Al/u.c., as indicated by the break
in the 6,=f[A1] plot, in agreement
I
II
with several analogous
1
/i/ I II O ZSM-5 observations reported (refs.
1 00 55L, h2 Y
p P0.AO I A ZSM-11 9,10,11). This observation allows
I
I us to state that A1 is not
I I I 1
randomly distributed in the
Allur. lattice but that its distribution
depends on its concentration.
Fig. 9. Variation of against [All for The break in (also in the signal
(A) ZSM-11 and (0) ZSM-5. width and the amount of xenon
adsorbed) for [A1]=2 Al/u.c. could
correspond to the presence or absence of an A1 atom at the channel
intersections. We would mention finally the difference between ZSM-5 and
ZSM-11 for [A1122 A1h.c..
228
TABLE 1
Chemical shift tis of 129Xe adsorbed on molecular sieves and characteristics of
the void spaces
--------~-----
Molecular sieve 6 s PPm Characteristics of the void space
A1P04-1
SAPO-11 I 120 Unidimensional channels, 10-ring
diameter: 3.9 x 6.3A
-
It is sometimes difficult to calculate 1 for certain structures and the
values are probably approximate (ZSM-5, ZSM-11 -and EU-1, etc.).
Nevertheless, we must remark that the experimental [tis,1 ] points are either
229
on the initial curve defined by Fraissard et a1 (ref. 5,6) (see Fig. 3-I), on a
curve parallel to the first one (Fig. 3-11) or, much more rarely, between the
two. More exactly, all the points corresponding to solids-with low or zero
cation concentration are located below curve I, for 0 . k 1 <3A. For a given
structure, when the xenon diffusion is very easy, the experimental points
are on the first curve, whatever the composition of the solid (zeolite Y and
SAPO-37). The points for AlP04-5, SAPO-5 and MAPO-5 are identical,
whereas those for erionite and AlP04-17 (same structure) are different.
Comparison of the 6 = f(n) curves of these two solids shows that xenon
diffusion appears to be easier in AlP04-17. In fact, the 6 increase, which is
linear in the first part of the curve, expresses the Xe-Xe interactions. For
erionite, 6 increases very little in this range. The passage from one cage to
another is easier in AlP04-17, perhaps because there are no cations, which
cause steric hindrance in erionite, or because of a more symmetrical opening
which requires less deformation of the xenon atom. Moreover, the xenon
adsorption rate is much greater for AlPO4-17.
If the same value of the mean free path
-i is assumed for AlP04-17 as for
erionite, the point of the coordinates [ 6 , , 1 ] is very much below the first
-
6,=f( 1 ) curve (Fig. 3-1). The value of the mean free path in the two solids
are not, of course, strictly identical; the Si-0 and P - 0 bond lengths are not
equal and the T-O-T angles must vary slightly from one compound to
another, which may explain the slight difference in the xenon diffusion.
Although we cannot explain in detail why there are two curves in Fig. 3,
they can be used to study zeolites and more generally all the porous solids
regardless of their composition.
PolvtvDe Y
We have studied two samples, denoted polytype Y-1 and polytype Y-2.
The polytype Y-1 sample shows no detectable defects. For polytype Y-2, the
230
crystallized free zone, a region where the pores are blocked or limited which
makes xenon diffusion more difficult.
ZSM-8
The spectra mostly consist of two signals corresponding to structures
ZSM-5 and ZSM-11. Table 2 summarizes the spectral characteristics and the
conclusions.
TABLE 2
Characteristics of the 129Xe-NMR on ZSM-8 and conclusions
I _ - ~ - - ----
Si/AI Spectral characteristics Conclusion
CONCLUSION
These complementary studies indicate more exactly what experimental
conditions should be used for the 129Xe-NMR technique, depending on the
nature of t h e sample and the property studied. This technique is
increasingly able to provide original results difficult to obtain by other
methods.
1 T. Ito and J. Fraissard, NMR study of the interaction between xenon and
zeolites A, X and Y, in: L.V.C. Rees (Ed.), Proc. 5th Int. Conf. on Zeolites,
Naples, Italy, June 2-6, 1980, Heyden, London, 1980, pp. 510-515.
2 J. Fraissard and T. Ito, 129Xe n.m.r. study of adsorbed xenon: A new
method for studying zeolites and metal-zeolites, Zeolites, 8 (1988) 350-
36 1 , (and references therein).
3 T. Ito and J. Fraissard, 129x8 nuclear magnetic resonance study of xenon
adsorbed on zeolite NaY exchanged with alkali-metal and alkaline-earth
cations, J. Chem. SOC.,Faraday Trans. 1, 83 (1987) 451-462.
4 A. Gedeon, J.L. Bonardet, T. Ito and J. Fraissard, Application of 129Xe NMR
to the study of Ni2+Y zeolites, J. Phys. Chem.. 93 (1989) 2563-2569.
5 J. Demarquay and J. Fraissard, 129Xe NMR of xenon adsorbed on zeolites.
Relationship between the chemical shift and the void space, Chem. Phys.
Letters, 136 (1987) 314-318.
232
A. Transient Measurements
A2 Flux measurements
- Time lag measurements for diffusion through a membrane
- Transient Wicke-Kallenbach
A3 Uptake rate measurements. (Following the variation of the mean sorbate
concentration averaged over a particle).
- Batch methods (gravimetric, volumetric, piezometric, frequency
response)
- Flow methods (chromatography, ZLC etc.)
EXPERIMENTAL METHODS
Gravimetric
Gravimetric uptake rate measurements were performed in a Cahn vacuum
microbalance systems, using small zeolite samples (10-12 mg) with incremental
pressure steps (to avoid the problems associated with the analysis of integral
uptake rate data). To maximize heat transfer and minimize external mass transfer
resistances, the zeolite sample was spread as thinly as possible over the balance
pan. Where possible, measurements were repeated with different crystal sizes and
different adsorbent sample configurations in order to confirm the dominance of
intracrystalline resistance. In the experiments reported here the volume of the
system was sufficiently large relative to the quantity of sorbent that the
sorbate pressure, following the initial step, remained essentially constant. The
simple expressions for the uptake curve for an infinite isothermal system were
235
m m
Parallel-sided Slab: -t-- 1 - -8 I -exp[-(Zn+l) 2 2 2
n Dt/4?. 1 (2)
(half-thickness 1 ) mm n2 n=O (2n+1)
-
ZLC
In the zero length column (ZLC) meth~d(~-~)
a small sample of zeolite
crystals (- 2 mg) held between two sinter discs, is equilibrated with sorbate and
then purged with helium (or argon) at a high flow rate. The hydrocarbon content
of the effluent stream is monitored continuously using a chromatography detector
(thermal conductivity or flame ionization). The conditions of the experiment are
adjusted to ensure that the desorption rate is controlled by diffusion out of the
crystals, rather than by the purge rate. This may be achieved by using a
sufficiently high purge flow. The absence of significant external resistance may
be confirmed by replicate measurements with He and Ar as the purge gases and the
dominance of intracrystalline diffusion may be confirmed by varying the crystal
size.
The mathematical model used to interpret the ZLC desorption curves assumes a
linear isothermal system with perfect mixing through the thin bed and adsorption
equilibrium maintained at the crystal surface. For such a system the desorption
curve (for a set of uniform spherical particles) is given by:
m - pn2Dt/R2
- -- 2 L I (3)
0 n=l [ p t~(L-1)1
n
For large values of L, pn + nv and Eq. 3 reduces, in the long time region to:
The diffusional time constant is readily found from the slope of a plot of log
(c/co) vs t.
If external film resistance is significant the analysis remains the same
except that the expression for L (Eq. 5 ) is replaced by:
236
It is evident that external film resistance may modify the intercept of the
semilog plot of c/co vs t but it has no effect on the limiting slope.
For a parallel sided slab of half-thickness Q, the expressions corresponding
to Eqs. 3-6 are:
-a 2Dt/Q2
m n
-= 2L
0
z e
n=l [an2+L(L+1)1
For large L, an (2ntl)n/2 and Eq. 8 reduces, in the long time region, to:
+
-r- 2 2
-n Dt/4Q
2
co (Ltl) e (10)
8
E 8 p=0-0.103 Torr
'- 0.1
1
E
-
\ PX, p=0;0.12 To;r , , ,
~/12.~~10-3
0.01
0 10 20 30 LO 50 60 70
Time (rnins)
Figure 1 Gravimetric uptake curves at 125OC ( % = 20 vm).
1 I I I I
Table 2
Summary of ZLC Diffusivity Data for Aromatic
Hydrocarbons in Silicalite Crystals
p - Xylene 80 60 11 2.8
80 100 23 2.9
100 60 37 4.1 30
150 60 55.6 11.9
150 (Ar) 60 40.0 11.8
200 60 51.3 43
In ref.(7) the ZLC data for benzene were interpreted according to the spherical
particle model. These values have been recalculated based on the parallel sided
slab model for consistency with the xylene data.
Figure 3 shows a comparison between the ZLC data and the gravimetric values
(extrapolated to zero concentration). It is evident that the agreement is
satisfactory. There is little difference in diffusivity between benzene and
p-xylene and the diffusional activation energies are all similar (- 30 kJ/mol).
In contrast with the results of earlier studies, the present data show no
evidence of any significant deviation from the simple diffusion model and the
differences in diffusivity between the C8 isomers are much smaller than has been
previously rep~rted.(~*~)The similarity in the activation energies implies that
the difference in diffusivity cannot be attributed to differences in repulsive
interaction energies resulting from the difference in critical molecular
diameters.
239
ZLC data are at zero concentration; NMR data extrapolated to zero from data at
higher concentrations.
240
I .
:.
; * 0 5A ( 55 pm) 1
'.4- '..*
i 0 13X ( 1 0 0 pm)
I
.I;
1 A 13x ( 50 pm)
~
1
ClCO
.01
,001
0 10 20 30
t (I)
4 5 6 4 5 6
1 0 ~ 1 (~
K1)
*
where uz and uz represent the potential energies of a molecule within the cage
(equilibrium state) and within the window (transition state). To avoid the
difficulties associated with the evaluation of the partition function for a
molecule within the cage (f,) one may make use of the equilibrium relationship:
-AHo/kT fZ (ug-uz)/kT
K = K e =- (12)
kT'Fe
B
where ug is the potential energy for the vapour phase (zero), thus obtaining:
.b
2 -1 2 -1
(molecule/ (kJ/nole) (a.s ) (an .s )
cage.Torr)
Ar-4A 3.2 p (Linde) 1.06 14 4.4 1.2 3.7 24.2 grav. (15)
Derrah
mmmtaic Kr-4A 3.2 rn ( L i d ) 1.26 17.7 1.2 0.12 10 33.8 grw.
tqs' CF4-5A 3.6 p (Lindc) 0.38 24.7 3.7 2.5 1.5 3.8 grav.
0 10 20 30 40 50 60
Concent rot ion (mg/g)
-
Gravirnetric Data,
10-12 ' 1 ' 1 ' I I ' ' ' ' ' '
1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
1 0 ~ 1 (K-')
~
Table 5
Critical Molecular Diameters of Some Aromatics Molecules
Diameter A
Benzene 6.9
Toluene 6.9
p-Xylene 6.9
o-Xylene 7.3
Naphthalene 7.3
2-6,2-7 DMN 7.3
1-2,l-5,1-6 DMN 7.9
1-3 DMN 8.6
1-4 DMN 9.1
Mesitylene 8.4
Tri-isopropylbenzene 9.3
Notation
c/co ratio of outlet concentration to initial concentration in ZLC experiment
D diffusivity (intracrystalline) (cm2.s-1)
References
W.M. MElER
Institute of Crystallography, ETH Zurich, 8092 Zurich, Switzerland
ABSTRACT
INTRODUCTION
For over two decades the 'Atlas of Zeolite Structure Types' (refs. 1,2) and its
forerunner (ref. 3) have reflected the
enormous progress made in the
elucidation of the framework structures
of zeolites and zeolite-like materials.
Fig. 1 shows that the current growth
rate of over 6 new structure types
per year is quite unprecedented. What
looks like an exponential growth is due
to two developments:
(a) the recent advances in the methods
of crystal structure analysis, in
particular powder diffraction
methods (refs. 4,5), and
(b) the greatly expanded range of
compositions of zeolite-type
"I
53
I
61
The following account describes some examples of uses of the Atlas which were not
dealt with previously (ref. 11).
Table I also shows that while the present structure-orientedactivity is greatest in the
field of phosphates, the silicates still make up the majority of zeolite structure types.
The structure types which have been approved by the IZA Structure Commission (SC)
since the last Atlas appeared in 1988 have been marked by a plus (+) in the Table. In
addition to these, seven structure types (listed in Table I) are under consideration for
clearance by the SC at present. A current listing of the zeolite structure type codes
can be found in the Appendix.
249
TABLE 1
1988. The gap defining the boundary between microporous and dense networks has
gained further support by the new data, and the postulated range for zeolite-type
materials has been confirmed. A particularly noteworthy addition is the data point
relating to ZSM-18 (MEI), the second framework containing 3-rings, which was
reported only recently (ref. 15). Earlier, only lovdarite, a beryllosilicate, was known to
contain 3-rings. The new structure type ME1 is very significant for it demonstrates that
silica can also form tetrahedral nets containing 3-rings (without Be being needed).
T-atoms / nm3
This bodes well for the synthesis of low-density materials based on 3-ring structures in
the silica field.
The FD is obviously related to the pore volume but does not reflect the size of the
pore openings. Customary values are frequently given or assumed for the free
diameters of channels with 8-, 10- and 12-ring apertures. It should be clear from Fig. 3
(which is also based on Atlas data) that the crystallographic free diameters for the
various types of apertures fall into a wide range. There is even a considerable overlap
of the respective ranges for 8-, 10- and 12-ring openings. Hence, sorption properties
have to be interpreted with caution when predicting the type of ring openings in
structurally unknown materials.
...._
18-ring aperture I......
li
........
14-ring i........
l i
#
12-ring
I
1O-ring [ 15 J
...........
9-ring ...........
1 2 :
8-ring
The customary values for 8-, 10- and 12-rings (applying to LTA-, MFI- and FAU-type
materials) are marked by arrows in Fig. 3. This Figure also includes relevant data for
VPI-5 with 18-ring channels (refs. 16-18) and for AIP04-8 with 14-ring channels
(ref. 19). These are the most open framework structures to date, and both have
unidimensional channel systems.
SOME MISCONCEPTIONS
Among the most widespread misconception is the belief that large unit cell
constants are indicative of large apertures. Fig. 4 should make it clear that there is
no such correlation, no matter whether minimum or maximum unit cell constants are
considered.
LTN-
LTN-
PAU- -
-
AFS-
FAU-
-
A more serious illusion is the belief that close resemblance between powder
diffraction patterns is sufficient to assign a structure type. This may hold in some
special cases. In general, however, the assignment or the establishing of a structure
type based on the similarity of XRD powder patterns is full of pitfalls. This has become
evident in a number of instances. For example, PHI and GIS were confused for well
over a decade, and later EAB and ERI were repeatedly mixed up. In one instance,
even the Structure Commission assigned a code to a structure type which turned out
to be in error (ref. 20). The code ATF of the erroneous structure type of AIP04-25 had
to be discredited, and according to the rules of the SC is not to be used again. The
correct structure has been assigned the code ATV. DLS is certainly an indispensable
tool for simulating and evaluating possible framework structures but a reasonable
agreement between an experimental XRD pattern and one based on DLS atom
coordinates does not give enough evidence for the correctness of a framework
topology. Even in cases in which this qualitative approach led to basically correct
framework topologies subsequent refinements have invariably revealed significant
differences. A good example of this kind is ZSM-12 (refs. 21,22). In the originally
proposed structure the channel dimensions were 5.5 x 5.9 A but structure refinement
later on showed these to be 5.6 x 7.7 A.
The utility and significance of loop configurations (LC) has been demonstrated
before (ref. 11). In a study on the evaluation of hypothetical zeolite frameworks,
Brunner (ref. 23) determined the relative abundance of various possible LC. One of
the more frequently occurring LC consists of a pair of edge-sharing 4-Yktgs. This is
shown in Fig. 5 together with two pertinent conformations. While the 'cis' conformation
(i) had been observed in 22 known zeolite frameworks, the 'trans' conformation (ii)
had not been recorded but was noted to occur in the proposed framework for VPI-5.
Brunner's findings cast some doubt on the correctness of the VPI-5 framework
structure at an early stage. Meanwhile, it has been found by extensive structure
refinements and NMR studies that the VPI-5 framework is not purely tetrahedral
(ref. 18). Instead, it is 4-connected (containing some octahedral At) and it even
appears that a strictly tetrahedral network of this type is unlikely to be obtainable.
254
For a considerable proportion of the frameworks covered in the Atlas, fault planes
have been listed. This allows predictions at a glance as to the likelihood of stacking
faults, twinning, and disorder. These possible defects are of considerable importance
in the characertistics of these materials and their catalytic applications.
OUTLOOK
ACKNOWLEDGEMENTS
The author thanks Dr. Lynne B. McCusker and other members of his group for
helpful discussions. Continued support by the Swiss National Science Foundation
(grant 20-25256.88 at present) is also gratefully acknowledged.
255
Appendix
REFERENCES
1 W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types (IZA Structure
Commission, 1978).
2 W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types, Second extended
edition, Buttetworths, 1988.
3 W.M. Meier and D.H. Olson, Adv. Chem. Series, 101 (1970) 155-168.
4 Ch. Baerlocher, Zeolites, 6 (1986) 325-333.
5 L.B. McCusker, Acta Cryst. (in preparation).
6 S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan and E.M. Flanigen,
J. Am. Chem. SOC.,104 (1982) 1146-1147.
7 B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan and E.M. Flanigen,
J. Am. Chem. SOC.,106 (1984) 6092-6093.
8 E.M. Flanigen, B.M. Lok, R.L. Patton and S.T. Wilson, Proc. 7th Int. Zeolite Conf.,
Tokyo (Elsevier, 1986) 103-112.
9 W.J. Mortier, Compilation of Extra-Framework Sites in Zeolites. Butterworths
(1982), pp. 67.
10 R. von Ballmoos and J.B. Higgins, Collection of Simulated XRD Powder
Patterns for Zeolites. Zeolite Special Issue 10 (1990) 313s-514s.
11 W.M. Meier, Studies in Surface Science and Catalysis, 49 (1989) 691-699.
12 R. Bialek, W.M. Meier, M. Davis and M.J. Annen, Zeolites (submitted for
publication).
13 G.O. Brunner and W.M. Meier, Nature, 337 (1989) 146-147.
14 M.E. Davis, Nature, 337 (1989) 117.
15 S.L. Lawton and W.J. Rohrbaugh, Science, 247 (1990) 1319-1322.
16 C.E. Crowder, J.M. Garces and M.E. Davis, Advances in X-ray Analysis, 32
(1988) 507-514.
17 J.W. Richardson, Jr., J.V. Smith and J.J. Pluth, J. Phys. Chem., 93 (1989)
8212-8219.
18 L.B. McCusker, Ch. Baerlocher, E. Jahn and M. Buelow, Zeolites (submitted
for publication).
19 R.M. Dessau, J.L. Schlenker and J.B. Higgins, Zeolites, 10 (1990) 522-524.
20 J.W. Richardson, Jr., J.V. Smith and J.J. Pluth, J. Phys. Chem., 94 (1990)
in press.
21 R.B. LaPierre, A.C. Rohrman, J.L. Schlenker, J.D. Wood, M.K. Rubin and
W.J. Rohrbaugh, Zeolites, 5 (1985) 346-348.
22 C.A. Fyfe, H. Gies, G.T. Kokotailo, B. Marlerand D.E. Cox, J. Phys. Chem. 94
(1990) 3718-3721.
23 G.O. Brunner, Zeolites, 10 (1990) 612-614.
24 J.M. Newsam and M.M. Treacy, Zeofile, in preparation.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 251
0 1991 Elsevier Science Publishers B.V., Amsterdam
Richard M. Barrer
Chemistry Department, Imperial College, London, SW7 2AZ, United Kingdom
ABSTRACT
Steady flow through a porous cystal membrane is associated with concentration
distributions across the gas/crystal interfaces which cannot represent true equilibrium. Steady
state distributions have been modelled from mass balance equations for a membrane where a
fraction of the flow enters the crystal directly from the gas phase and the remainder enters via
an externally adsorbed layer. The same fractions are assumed for the nett flow through the
exit surface. Special cases of the general equations investigated numerically or otherwise
include : the extent of departures from equilibrium across interfaces; the ideal flow when these
departures tend to zero; the ratios of ideal to measured flows; and ratios of true intracrystalline
diffusivities to apparent diffusivities obtained from steady flows by assuming equilibrium
across interfaces. In fast sorptions and desorptions non-equilibrium distributions across the
gas/solid interface may also result in differences between true intracrystalline diffusivities and
those obtained by incorrectly assuming equilibrium.
INTRODUCTION
Zeolite membranes provide in principle a means of continuous scparation based on
differences in the shapes and sizes of molecules. If they contain catalytic centres they can also
be envisaged as membrane reactors. In steady flow, independently of any model, more
molecules of diffusant enter the crystal than leave at the ingoing surface. T h a c imbalances
require that concentrations just within the crystal cannot have their equilibrium values (ref. 1)
at either surface, so that it is of interest to examine their scale. The imbalances have recently
been modelled quantitatively for gases obeying Langmuir's isotherm when all molecules enter
the crystal via an externally adsorbed layer (ref. 2). In this paper the model will be extended to
include, for very wide windows, possible entry directly from the gas phase simultaneously with
entry from the externally adsorbed layer. Also considered is the effect of imbalance betwecn
forward and reverse flows across the gas/crystal interface in transient state sorption and
desorption kinetics. Aspects of surface resistances have already formed the bases of other
papers (refs. 3-5).
The treatment for a single crystal applies also to membrana consisting of a monolayer of
porous crystals on a macroporous support, in which gaps between porous crystals in the
monolayer are filled by a non-permeable medium which adheres permanently to the sides of
the crystals, but leaves their top and bottom surfaces free of the adhesive. In another kind of
membrane the porous crystals comprise a discontinuous phase embedded in a continuum. Such
membranes will not be considered here.
258
(a)
GAS CRYSTAL GAS
%
x= 0
el
DISTANCE - %-I 9n
x=l
(b)
GAS CRYSTAL GAS
AE
x=o
DISTANCE - x =I
Fig. I . (a) The energydistanre curve for entry to the rrystal from an externally adsorlml
layer. ( b ) The energv4istance curve alien entry to tlic crystal takes plare directly froin t l w
gas phase.
C C denote constant Concentrations in the gas phase at x = 0 and x = Ircspertively.
go’ gl
Oo , @,denote fractions of external sites of type A occupied at x = 0 and x = 1 respectively.
O1. On denote fractions of internal sites occupied a t x = 0 and x = I respcctively.
.
E, E, denote activation energies for entry from external sites and for intracrystalline diffusioii
rcsprtively.
AEs , AE are energies of dcsorption from sites of type A and from intrarrystallinr sites
respcctivrly.
259
MODEL
Sorption is assumed to obey Langmuir's isotherm for which diffusivity is independent of
concentration (ref. 6). A single crystal membrane, bounded by planes x = 0 and x = 1 separates
a constant gas phase concentration C at x = 1, with C > C Inside the crystal activatcd
d go gr
diffusion occurs involving energy harriers of height El. Molecules of diffusant may enter or
leave the crystals via an externally adsorbed layer, for which the cncrgy of desorption is A E ~ .
Fig. l a shows the energy - distancc configuration, the energy levels and the nomenclaturc
involvcd. If the windows are widc cnough some moleculcs may pass directly from the gas phase
to intracrystalline sites, for which the energy - distance curves and nomenclature are shown in
Fig. lb. Of the nett flow J through unit area of surface the fraction F2 J occurs as in Fig. l a
and a fraction F1 J as in Fig. lb, wlicre (F1 + F2) = 1.
A t and around channel mouths at x = 0 there are sites of type A from which the molecules
comprising F2 J enter the crystal and possibly sites of type I3 from which they do not. There is
however constant exchange of molecules between the two kinds of site and between each kind ol
site and the gas phase. In steady flow there is nett transport f2 J from the gas to the B-typc
sites and hcncc from B- to A-type sitcs. There is also nctt transport of fl J from the gas phase
to sites of type A and therefore (fl + f2) J = F2 J from these sitcs to the interior of the crystal.
In addition there is nett transport F1 J from the gas phase directly into the crystal. These
mechanisms are shown schematically in Fig. 2.
Entrv at x = 0 Exit at x =I
Gas Phase Sit,esesp
F1 7 /Sites A<-Sitf2es J B
li2J
Sites 1
Fig. 2. Mechanisms of cntry to and exit from the porous crystal mcmbrane.
whcre s is the number of energy barriers of hcight El pcr unit arca in each of (n-1) planes
normal to x and k = kl exp (-El/RT) is the rate constant for jumping from onc energy well
over the barrier El to the next well. (n - 1) per channel denotes the number of barriers
bctwcen x = 0 and x = 1 and n is the corresponding number of cncrgy wells (i.e. sorption sites).
O1 and On are the fractional occupancies of sites 1 just within thc crystal at x = 0 and of sites n
just within the crystal at x = 1. They are not equilibrium but steady state values. To find
them the processes of Fig. 2 at and across the gas/solid interface must be considcrcd.
(13)
cxprcssion at x = lis
M'itlioiit going through all the sleps, equations 6 and 7 with the aid of the eqnations S to 14 can
bc transformed to the cxnressions
wlicre
r = cxp [(AE- AEs +Es)/ItT]
A= ( k b / k d ) ~ p [ ( -AEs)/RT]
E~
Equations 15 and 16 show that O1 < OlCq and On > 0 , and that the tliffcrcnccs
nccl
(Ole(, - 01)and (On - 0 ) are not equal except, in the IIcnry's law rangc. Equations 15 and
ncq
16 also show that the imbalanccs (Olcc, - O1) and (Oil - 0ncq ) increasc as the flow J through
unit area increases, i.e. as the permeability increasrs.
When f l J / y C in equations 13 and 14 is << 1 0,-> 0 and o1-> Olcq. \I'hcn
a g ocrl
O0 antl O1in equations 6 and 7 arc respectively replaced hy 0 and 0 thc tcrms involving
ocq kq
f l J/yaCg i n eqnations 15 and 16 do not appear and tliese equations become
262
(20)
If O1 and On in equation 1 are replaced using equations 15 antl 16 tlic result is a cubic i n J.
When this substitution is made using cquations 19 and 20, on the other hand, one obtains lJie
linear equation
- Sk (21)
('lcq - 'neq) = id
Jid is the value of J when the second terms on the r.1i.s of equations 19 and 20 arc respectively
<< 0 1ecl and << OIlet1, i.e. when 0 1 -> Ole(, antl 0 I1 -> 0 neq'
+
kl'(1 - Ole )
- sk
+ ( l - ooeti)l
- (n-I)(Qleq
'(11
-Oncq) = J id
sk [ I ' / S k d
-1) [ A + (I< -
I<fl/ya]
K s ) f l J/ya + 1
1
(23)
Equation 23 is a qiiatlratic i n J. Important quantities inclutle Jitl, J i d / J antl f l .J/y C wliicli
a 6'
will lx considered in turn.
Estimation of Jid
Jitl was estimated in reference 2 for assigned values of I<C and of C /C which was
go' go @
taken to be 100. I n equations 21 or 23 k = k l cxp (-lC1/RT) and k l N vx, the vibration
frequency in the xedirection of the sorhctl niolcciile rclat.ive to it,s site. The value a.ssigiietl was
12 -1 3
5 x 10 s . The number of sites, s, per tin- just within the crystal was cqiiatctl with tlic
2
number of windows per cm . This number was calculated previously for a series of zrolitcs (ref.
2) antl the value 5 x 1013 was taken (corrcct for ZShl-5). This may be a lower limit for s
because just within each window tlicrc ma,y he several sites. For ( n -1) we have
(n -1) = l/d (24)
wliere d , the jump distance per unit, tlirfiision st,ep, wa.s t,a.ken as 5 x 10-8cm and 1 as 10-2cm,
which is close to t,he values i n recent siriglc crystal memhrane studies (rcfs.7-9).
263
Tlie calculatcd values of Jid are reproduced i n Table 1 for several values of I<C and of
go
El/Rr. Table 1 indicatcs thc extreme sensitivity of Jid to the activation encrgy El and
temperature T , as indicatcd by tlic ratio E I / R T , and it suggests tlie scale of tlic ideal flows
which the crystal could generate. For a menibranc consisting of a monolayer of crystals, with
intcr-crystal gaps filled by an impermeablc substance, an active arca of 100 m 2 of crystal
surface would increase the throrigliputs by a factor of lo6 , but the fabrication of such
iiicnibrancs is so far an unsolved problem. At T = 301.9K the activation energies, El, in tlic
Tahle would be 9, 6, 4.2 and 3 kcal mol-I and at 90K these cncrgies would bc 2.6S, 1.79, 1.20
and 0.S9 kcal mot-' respectively. The maximum flow is found when K C = (C / C
go go g l *
TABLE 1
Jitl (cm3 at s.t.p. l~-1cm-2) for parametcrs assigiied in the text and for scvcral values of
KC and E1/RT. C /C = 100
go go .@
TABLE 2
Particular cases of equations %G and 27
Conditions J .I tl / J (cqn.26)
tl
I:] = 1; 0 << 1 l - t 7 ( 2 - - 0 1cq ) exp [(AE - E,)/RT]
ncq
FI = 1; Olcq, 0 < < 1 +
1 2tl esp [ ( A E - E l ) / R T ]
ncq 7-
1 + (skll\f / y a )
(I\ -
CX~, [(AEs
I\7s) f , J / T ,
-
+
A15 - E,)/RT]
1 I (35)
265
Several special cases arc suinmarisctl i n l’able 2, i n which 6AE = (AE - AEs + Es - E l ) , and
so is the difference hctwccn tlic a c t i v a t h energy for desorption from within the crystal to the
cstcriially adsorbed layer, ( A E - AEs + Es) , (sce Fig. la) and the activation energy for
intracrystalline diffusion, El. In all tlic expressions in Table 2 the terms ((I/[) cxp (6AE/RT)
or ((I/[) cxp ( A E - E1)/RT appear. Their numcrical cvaluation shows t1ra.t thcsc terms can be
vcry large down to very small (Tahle 3). I f tlir former, J will he much less than Jid; if thr
Iatt.cr, J.Id /.I -> 1. The values EAE must Iiavc, at. several temperatures, to givc thc valucs of
(d/l) cxp (EAE/RT) in the second column arc shown in the last five columns of Table 3. I t is
notktl t1ia.t 2/(n - 1) = 2d/l is tlic ratio of tlic numl)cr of harriers across thc two interfaces a t x
= 0 antl x = 1 to the numbcr of intracryst.allinc barriers.
I n Table 4 (ref. 2) values of J.I d /.I are given, according to equation 31, with tl = 5 x 10-scni
antl C / Cg l = 10. The figures crnpliasisr again that low tcinpcratrircs and vcry sinall
go
crgstallitcs will favow high valurs of .Iitl /.I and convcrsrly thc higlrcr the tcmpcraturc and the
n
Iilrger tlic crystal tlic iriorc iicarly will .litl /.J approac1i unity. TIIUS,for I = 10-”cin ant1 at ~ O K
.J is rnuclr less than Jitl /.I for all EAE > 2 kcal inol-l , and if 1 = 10-2cm the sa1iic is true for all
6AE 2 3.0 kcal mol-’ . A t 301.91i, oil tlre other liantl, .I.Id / J is vcry close or close to unity for
all l i a ~< 6.0 kcal rno1-l . Large values of ME could inc~ica.tepartial blockage of wintlows
giving access to t,lie int.rrior of the crystal due to special causes (refs. 3-5).
266
Estimation of fl J/Y& Cg
I n deriving equation 26 it was assumed that Oo = 0 and Q I = Okq, so tlial i n eqwitions
oeq
13 and 14 f l J/X. C must be << I . This assumption will now he examined.
h g
2
y C is the number of molccnlcs per second per cm that are adsorbed on sites of type A
a g
(at or around channel mouths). l'liis numhcr will bc less than hut of thc same order as the
nnrnhcr of collisions per second per cni2 . This collision numhcr is C c/4 whcrc c is the average
g
spcctl of a molecule, so that ya is less than but tlic same order as c/4. Likewise f l will be less
hut of the same order as unity so that a reasonable approximation to f l J / y C will be 4.J/tC' .
" g g
The maximum value of this term is 4JiCl/CC . .JiCl can be taken from Table I , after conversion
6
-I cni-2
to niolcculcs s . C is i n molcciilcs cni-"' and the avrrage spcctl in cni s-I. Tallle 5
g
gives values of c for a number of gases as well as the collision nninlxrs (molecnlcs s -'cm -2)
according to the ideal gas law at one atmosphere pressure.
TABLE 4
Jitl/.J according to cqnation 31(') for different values of I<C and bAE (kcal n7oI-l). C / C
= 1o and (I = 5 x 1o -'
cm
go go )gl
Argon may be taken from Table 5 as a sample diffusant. Then in steady flow through
single crystal membranes one obtains for 4Jid /C C the values in Table 6. The mcmhrancs
g
have been assigned a nuinher of values of El /RT and there is a range in KC In each case
go'
C has the value appropriate for 1 atm pressure at the temperatures T = 90K or 301.91<, and
go
Cgo /Cg,is 100. Other parameters uscd in estimating Jid were: 1 = 10-2 cm; (1 = 5 x 1012 5 -1
aiid s = 5 x 1013~ m - ~
as ,for Table 1. Clearly at 1 atm one is well justified i n taking
0 =0 , and, with C = lo-' C as i n Table 6 , one is also justified in taking
o oeq gl 60
0 1-- 0 Pq'
I n equation 27 , which is applicable wlicn a near varitiim is maintained on the exit side of
tlie nicnil~ranc,the tcim [(I< - KS)( f l J/ya) + 11 arises. The cqiiation is simplifictl if it can he
shown that ( K -I$) ( f l lily,) is << 1. As previottsly, we assitme f1/ya-4/C and the flow, .J,
is replaced by its maximiim value, .lid . For the rlioscn valucs of KC the Langmuit
g
eqtiilil~riumconstant, I<, was found when the pressure at the ingoing face of tlie crystal was
taken as 1 atm. At this pressitre for the ideal gas C = 2.431 x lo1' rnoleculcs c 1 ~ 1 -at~ 301.91<
g
arid S.155 x 10 I9' at 9OK. If one then again t a k a the average speed, C, for A r from Table 5 as
the example the valrtes of 41</c-fl ate those i n Tablc 7.
268
TABLE 6
4 J i d / t Cgo for Ar at 90K and 301.9K ,for membranes having the parameters givrn i n the text
and with C / C = 100.
go gl
50 0.6471 90 0 . 5 5 5 ~ 1 0 - ~
301.9 1.O 17x lo-' 1.509x lo-'
0.8182 90 0.702x 1or9
301.9 1.2s6x10-9
5 0.7857 90 0.674~10-~
30 1.9 1.253~10-~
1 0.4901 90 0.42 1x I o-{)
301.9 0.772x.10-9
0.1 0.0899 90 0.077 1x 1 0-9
301.9 0.14 13x 10-9
Values of .lid were next calculal~ctlfor 1 atm pressure of tliffrisant at x = 0 and iicar-vaciiulr1 ill,
x = 1 (Omq -> 0). As iii Talde 1, the valrics of .Jicl at 90K (as molcciilcs s - ~ c I T - ~arc'
) sriclr
that 4 Jid K/c is always orders of inagnitutlc less f,lra.n 1 so that a fortiori the same' must be I r11e
of 4Jid (I< - Ks)/c. It therefore scciiis plol)able that the term (I< - I< ) f , l / can
~ ~be oiiiit.t.ctl
s 1
from equation 27, 34, and 35 untlcr inost, cspcriinciital contlitioas.
TABLE 7
Values of q u a n t i t i e s needed t o find 4Jid K/C f o r Ar. Ingoing pressure 1 atm.
J i n molecules s-l K i n molecules -' cm3., c- i.n cm s-'.
N
W
0)
270
‘1’a.blc 4 thcrcfore shows some conditions untlcr which Did/D greatly cxcccds or approaclics
app
unit,y. If equation 37 is used to int,crpret measured stcatly flows in terms of D a1w where .I.Id / J
cxceeds unity a variety of values of D coultl result in the same zeolite according to tho
aPl)
choice of variablcs which dctcrniine the extent of non+quilihrium across ttic gas/crystal
interface (inter alia I, T , C antl C ). As 1 and/or T increase tlic D will converge toward
go gl aPP
Did. Moreover, diffusivitics can vary among different samples of t,he same zrolito if thcsc
samples conta.in variable amounts of part.ial int,racrystallinc blockages, as considered i n ref. 2
for lkiimensional channcl systcnis.
From Jid = (skld/l) cxp (-El/R.T) (Olcq -Oncq) = Ditl CSat,(0leq - 0ncq )/[, whcrc
csat= s / ( ~is the npta.ke in molecules wlicii o= 1, wc Iiavc for tlic int.racrysta\linc
tliffusivity in an itlcal crystal:
I)icl = k l d 2 CXP (-E1/RT)
(39)
This expression is implicit in thc calcula.t.ion of -1.It1 i n ‘I’ahlcs 1 and 7. k l , tl a n d El will
vary according to the porous cryst.al antl the diffnsant. With the prcvioris assignnicnt,s k l = vx
= 9x s-’ and d = 5 x 10 -’ cm , D~~~for (liffcrcnt. valncs of E ~ / R Tis as follows:
El/lt?. 20 15 10 7 5 3.33
I)i(l/cnl‘Ls-l 2 . 6 ~ 1 0 - ~ ’ 3 . S ~ 1 0 - ~ . 5 . 7 ~ 1 0 - ~ 1 . 1 4 ~ 1 0 - ~ S . ~ X I O - ~4 . 5 ~ 1 0 ~ ’
El at 301.91<
12.0 9.0 6.0 4.2 3.0 2.0
kcal nio1-l
Thus the simple cqnation 39 yiclrls physically rc1asoiial)le valucs of I). id for t,hc ahovc clioice of
k l antl (I.
(i) The single crysthl niemhranc is i n sorpt,ion equilibrium wit,li the gas at, concent,ration
C At t = 0 , C at x = 0 only is inst,anta.neously raised to C and t.hc system
gf gl go’
t.licrcaftcr rclaxcs t,owartl the stcatly state of flow, wit.11 C and C licltl constknt. For
go d
greater simplicity, in place of cqiiat.ions 1.5 and 16, for the externally adsorhcd layers
271
it is assumed that 0 = 0
0 ocq and O1= OlCqas in equations 19 and 20. Tlicn
J 1 ( t ) = [OleC,- O1 (t)] R1 = - Csat D ( t l O / t l ~=
)~ (40)
and at x = 1
J n ( t ) = [On ( t ) - 0 neq ] R2 = -Csat D ( t l O / d ~ =
) ~1 (41)
The respective cocfficicnts, with the aid of equations 17, 18 and 25, bccomc
Ill =
did ( A +1 - OOe )
-
skl {F1 + F, (1 - OOe ) exp [ ( A E , - Es)/RT]}
( 1 - 0 1cq) ( 1 - 0 1c q ) exp (AEIRT) (42)
R =
skd ( A + -
+
1 - Ole ) skl {F1 F2 ( 1 - O l e ) e x p [ ( A E s - Es)/RT]}
I1 (1 - 0 ( 1 - 0n e q ) exp (43)
ncq)
Eqiialions 42 and 43 show thosc properties of a sorbatesorbent system which, in addition
to .J(t), will determine tlie differences between 0 and 0 ( t ) just within tlie crystal. The
cq
coefficients R1 or RI, arc the same for t,ransicnt, and steady flows and thcrcforc thc ratios
J1 ( t ) / [Oleq - 0 , (t)] or J n (1) / [On ( t ) - OnCq] arc constant for all t. If transient
solutions of Fick's second equation arc required they must satisfy tlic boundary condition
O1 = O1 ( t ) a.nt1 0n = 0n (1) for a.ll t > 0 (44)
ratlicr than solutions bascd upon the assumption
O1 = Olcq and OI1 = 0 for all t > 0 (15)
ncq
(ii) The sccontl example is that of sorption and tlcsorption kinctics, in which flow decays
from an initial niaximum va.luc to zero at eqiiilil~riiim. At time t = 0 for sorption the
concentration at x = 0 a.nd x = 1 is instantaneously raised from C to C and kcpt
gl go
constant at that value. Tlic system tliercafter relaxes from its prcvious sorption
equilibrium to t,hc new equilibrium. For a cryst,al with a I-dimensional channel system
parallel with the xdircctioii
J ( t ) = 0 = - J ( t ) = / = [@cq - 0 ( t ) ] R = -Csat D((l@/dx)x = 0 (46)
For tlcsorption, when at t = 0, C is instantancously lowered to C the corresponding
go .d
expression is
-J (1,) = 0 = J (t,) = 1= (0 ( t ) - 0 ] 0 = - C sa.t D ( t l B / d ~ ) ~ = (47)
C(l
I n tlirsc expressions a positive sign is given to J (t) whcre flow is in the direction of x
incrca.sing. The symmct,ry of tlic situation at each intcrfacc means that R1 = RI1 = R in
equations 42 and 43. Otherwise comments made for transicnt, flow in tlic membrane apply
equally to solption~llesorptionkinetics. Especially if J ( t ) is initially large the time
dependence of 0 ( t ) a n d its difference from 0 may be such that solut,ions of Fick's
ccl
second equation ba.scd on 0 = 0 for all t > 0 at x = 0 and x = 1 (equation 45) arc no
cq
212
CONCLIJDING REMARKS
It has becn the purpose of this paper antl its pictlecessor (ref. 2 ) to model the transpoit
piopcrtics of single crystal membranes taking into acconnt the processes occurring at and
acioss the mcmbiane surfaces as well as tliose witliin the crystal. In the present paper the
iiiotlel has hwn extentled to include the possibility of simultaneous entry to the crystal both via
an externally adsorbed lajer antl tliicctly fioin the gas phi1sr. Tlic role of tlic mass balance
equations across tlic surface has also 1w.w extentled to sorption~esorption kinetics.
273
I n t.hc previous paper (ref. 2) thc important role of partial blockagcs located along
l-dimcnsional ( 1 - D ) channcl systems was niodcllcd and examined numerically. The papcrs
show how the modcrating effect of the mass balance equations at and across mcmbranc surfaces
will increase with decreasing thickness and falling tempcraturc. Some numerical estimates
indicate that undcr conditions when the intcrface cffccts havc littlc influcncc upon flow at room
tcrnpcrature these effects may dominatc flow at low tcmpcraturcs, such as OOK. \Vliere flow is
reduccd by partial blockages distributed along 1 - D clianncls thc reduct.ion is indcpcndent of
membrane thickness and can be vcry large (ref. 2).
REFERENCES
1 R.M. Barrer, in "The structure and Propcrtics of porous Matcrials". Eds., D.H. Everett
and F.S. Stone, (Butterworth). 195S, p.170
2 R.M Barrcr, J.Chcm. SOC.Faraday Trans., 1990, SG, 1123.
3 M. Kocirik, P. Struvc, K. Fiedlcr and hi. Bulow, -1. Chcm. Soc. Faratlay Trans. I , lOSS, 81,
3001.
4 M. Kocirik, A . Zikanova, P. Struvc and hl. Bulow, i n "Zeolitcs: Facts, Fiqurcs, Future".
Eds. P . A . Jacobs and R.A. van Santcn (Elscvicr), 19S9, p.925.
5 J . Kargcr, II. Pfcifcr and W. Ileink, i n Proc., Gth Int. Zeolite Conferencc, Eds. D. Olson and
A. Bisio (Butterworth) 19S4, p.lS4.
G I1.M. Barrcr, Langmuir, 19S7,3, 309
7 D.L. Wernick and E.J. Osterhuher, i n Proc. 6th Int. Zcolite Confcrcncc, Etls. D. Olson and
A. Bisco (Butterworth) 1983, p.123.
S A. Paravar and D.T Hayhurst, in Proc. Gtli Int. Zcolitc Confcrcncc, Eds. D. Olson and A
Bisio (Buttcrworth) 1984, p.217.
9 D.T Hayhurst and A.R Paravar, Zcolitcs, ISSS,g, 27.
10 J.Crank, "Thc Mathematics of Diffusion" 2nd Edition, (Clarcntlon Prcss), 1975, pp.53, 75
and 92.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 275
1991 Elsevier Science Publishers B.V., Amsterdam
D.E.W. VAUGHAN
Exxon Research and Engineering Company,
Rt. 22 East, Annandale, New Jersey, U.S.A., 08801.
SUMMARY
The position is taken that the crystallization products of a gel are the
key to understanding the important gel intermediate structures and therefore
the mode of zeolite genesis. Reviewing the products of reactions in sodium
and potassium aluminosilicate gels leads to the conclusion that extended sheet
(Na) and columnar ( K ) sub-structures are the important structure building
units. The smaller base metal cation controls the nature of the sub-structure
and the larger cation the ways in which such units interconnect to form
specific zeolites.
INTRODUCTION
Much recent interest in modes of zeolite genesis has focused on the role
of small molecular clusters as major participatory species in the direction and
development of zeolite structure types, relying mainly on developments i n
such techniques as NMR (1,2,3) and Raman spectroscopy (4) combined with
increasingly powerful computer hardware and software capabilities which
facilitate infinite peak deconvolution and search-match abilities. S u c h
methods reveal much new information about the complexities of the silicate
and gel systems of interest, but they give little guidance to those researchers
interested in creating, and preferably tailoring, new zeolite structures.
Indeed, it is probable that species observed in solution during zeolite
crystallization are primarily "spectator species" in a state of dynamic near
equilibrium in a reactive system in which the "participatory species" are
constantly scavenged by the growing zeolite(s) or their structure additive
sub-units.
An alternative approach, examined i n part by Liebau for silicates i n
general ( 5 ) and by Barrer for zeolites i n particular (6), is to look at larger
216
GME
GIS MAZ
MER LTL
PHI OFF
MAZ
TABLE 1
Phase development with sodium as the primary cation
FAUJASITE ( F A 4
Pure 1 or pure 2
layer type 1
layer type 2
(mirror image of layer 1)
BRECK'S 'STRUCTURE 6' (BSS)
Alternating 1 and 2
base metal gel products. ECR-1 is a "boundary phase" between MAZ and MOR,
specifically templated by DMDE(0H) (21), these materials having structures
related as shown in Figure 3. The MAZ and MOR sheets may be connected in
two different ways, at c=O and 1/2, and it is possible that ECR-1 may be a
mixture of the two forms (22). Coherent overgrowths of MAZ on ECR-1 (8) and
MOR on MAZ have also been reported(23).
Apart from TMA inducing the formation of OFF and OFF/ERI mixtures
(ERI always the minor component), the alkylammonium gels produced mainly
282
LTL, frequently having relatively high Si/AI ratios near the limit of the Linde
L composition range of 2.6 to 3.45 (25). The presence of the alkyl ammonium
cations also greatly slow the sequential reaction to more dense products,
presumably by inhibiting the nucleation of the denser zeolites PHI and MER.
OFF and ERI may crystallize either as separate crystals (26) or as a crystalline
intergrowth of the Linde T type (27), but in these experiments they were not
differentiated.
TABLE 2
Phase development with potassium as the primary cation.
LTL and OFF are assembled from the same columns of double 6-ring
linked cancrinite cages and the ERI column is similar, differing only in a "flip"
in the cancrinite cage linkages, as shown i n Figure 4. Although much has been
made of the ABC 6-ring sheet stacking relationship of OFF and ERI (and many
other structures too (see ref. 28 for a good review)), LTL does not belong to
that structural group and would not therefore be expected as a c o -
crystallization product if such a sheet dominated the gel structure. The co-
crystallization of LTL and OFF/ERI with an apparent epitaxial interface in
hammer shaped crystal associations (with the hammer head LTL and shaft
OFF) requires a common interfacial structure (29).
283
Figure 4. The columnar structures and relationships in LTL, OFF and ERI.
Figure 5. In GIs, MER and PHI the same chain of 4-rings is connected in the
ways shown to form sheets which constitute the extended building unit.
284
DISCUSSION
The data discussed i n this paper represent three groups of related
zeolites which crystallize and often co-crystallize over a small range of
synthesis conditions - FAU/bss; MAZ/MOR/ECR-1; LTL/ERI/OFF. Their
associations can be better understood if the critical structure determining
units are seen as being much larger than the sbu small cluster groups
generally favoured as the important structure building units. In these cases
the structure of the extended structure (sheet, column, chain, etc) is
seemingly determined by the Group 1A base metal cation and the manner i n
which they join together is determined by the charge and configuration of the
larger secondary cation.
REFERENCES
1 . J.P.van den Berg, P.C.deJong-Versloot, J.Keijsper and M.F.M.Post, Stud.Surf.
Sci.Catal.#37, Eds. P.J.Grobet,W.J.Mortier, E.F.Vansant and G.Schulz-Ekloff,
Elsevier (Amsterdam), (1988) 85-95.
2 . G.lIarvey and L.S.Dent-Glasser, Am.Chem.Soc. Syrnp.Ser.#398, Ed.M.L.Occelli
and H.E.Robson, (1989) 49-65.
3. A.V.McCormick and A.T.Bell, Catal.Rev.Sci.Engrg.. 31 (1989) 97-127.
4. P.K.Dutta and D.C.Shieh, J.Phys.Chern., 90 (1986) 2331-4.
5 . F.Liebau, "Structural Chemistry of Silicates.", Ch. 7 and 8, Springer-Verlag.
(Berlin), (1985) pp.90-160.
6. R.M.Barrer, "Zeolite Structures" in "Zeolites: Science and Technology.". NATO
AS1 Series #80, Ed. F.R.Ribeiro et al, (1984) pp.35-82.
7. M.M.J.Treacy, J.M.Newsam, R.A.Beyerlein, M.E.Leonowicz and D.E.W.Vaughan,
J.Chem.Soc.Chem.Commun., (1986)1211.
8. M.E.Leonowicz and D.E.W.Vaughan, Nature, 329 (1987) 819.
9. J.M.Newsam, M.M.J.Treacy, D.E.W.Vaughan, K.G.Strohniaier and W.J.Mortier.
J.Chem.Soc.Chem.Commun., ( I 989) 403-4.
10. M.M.J.Treacy and J.M.Newsam, Nature, 332 (1988) 249.
1 1 . W.M.Meier and D.H.Olson, "Atlas of Zeolite Structure Types.", 1ZA/ Butter-
worths (London), ( 1 987).
12. D.E.W.Vaughan, "Microstructure and Properties of Catalysts.", MRS Symp.
Proc. 11 I , Eds. M.M.J.Treacy, J.hl.Thomas and J.M.White. (1988) 89-100.
13. P.B.Moore and J.V.Smith, Mineralog. Mag., 35 (1964) 1008-1014.
14. D.E.W.Vaughan and K.G.Strohmaier, in Proc. 7th.Intl. Zeolite Conf.. Stud.
Surf. Sci. Catal. #28, Ed. Y.Murakarni, A.lijirna and J.W.W;ird, (1986) 207-214.
15. 1I.L.Wadlinger and G.T.Kerr, US Patent 3,308,065, (l!lh7).
286
ABSTRACT
The paper p r e s e n t s a f u r t h e r development of s t u d i e s i n z e o l i t e
c r y s t a l l i z a t i o n k i n e t i c s c a r r i e d out e a r l i e r i n the l a b o r a t o r y
of t h e authors. It was shown t h a t by performing a j o i n t a n a l y s i s
of c r y s t a l l i z a t i o n curves d e s c r i b i n g z e o l i t e c r y s t a l growth i n
a l u m i n o s i l i c a t e g e l s i n t h e process of t h e i r hydrothermal cry-
s t a l l i z a t i o n and of d a t a on s i z e d i s t r i b u t i o n z e o l i t e c r y s t a l s
i n t h e f i n a l products of g e l c r y s t a l l i z a t i o n i n combination with
t h e i r pretreatment at d i f f e r e n t temperatures before subsequent
isothermal c r y s t a l l i z a t i o n , one can a t t a c k t h e problem of
studying temperature dependences of z e o l i t e n u c l e a t i o n r a t e i n
t h e c r y s t a l l i z i n g gels.
INTRODIJCT I O N
Since experimental s t u d i e s s t a r t e d publishing t h e k i n e t i c s
of z e o l i t e s c r y s t a l l i z a t i o n /1/ and up t o our days, t h e constru-
c t i o n of S-shaped k i n e t i c curves d e s c r i b i n g t h e growth of z e o l i -
t e mass i n t h e process of a l u m i n o s i l i c a t e g e l s isothermal cry-
s t a l l i z a t i o n h a s remained t h e most common method of d i s p l a y i n g
experimental r e s u l t s of such i n v e s t i g a t i o n s . These k i n e t i c depen-
dences a r e i n most c a s e s w e l l described formally by t h e following
equation:
Zt/Zf = Z = ( 1 - e-ktn) (1 1
where Zt - mass of c r y s t a l s i n t h e c r y s t a l l i z a t i o n product which
were formed during t h e time t from t h e beginning of c r y s t a l l i -
z a t i o n ; Zf - mass of c r y s t a l s i n t h e f i n a l c r y s t a l l i z a t i o n pro-
duct; k and n - dimensionless c o n s t a n t s depending on g e l com-
p o s i t i o n s , temperature and some o t h e r c r y s t a l l i z a t i o n c o n d i t i o n s
(seed, g e l ageing e t c . ) . However, such curves do not b e a r any
information on t h e b a s i c k i n e t i c parameters of c r y s t a l l i z a t i o n :
l i n e a r r a t e of c r y s t a l growth and n u c l e a t i o n rate.
The p o s s i b i l i t y of experimental s t u d i e s of t h e s e parameters
f o r r e a l conditions of z e o l i t e c r y s t a l l i z a t i o n on t h e example of
a Due t o i l l n e s s o f Prof. Zhdanov the paper could not be presented i n Leipzig.
288
SXPXRIT':SrJT
The a l u m i n o s i l i c a t e g e l s s t u d i e d were of t h e f o l l o w i n g compo-
s i t i o n s : 2,76 Na20 A1203 1,91 Si02 409 H20 and 3 , 7 2 Na20'
4.l2O3 . 2,8 S O 2 351 H20 t h e f i r s t of them c r y s t a l l i z i n g i n t o
Na-A z e o l i t e s , t h e second i n t o Na-X ones. A l u m i n o s i l i c a t e g e l s
were p r e p a r e d by mixing a l k a l i n e s o l u t i o n s o f sodium s i l i c a t e
0
and a l u m i n a t e end were c r y s t a l l i z e d at 90 C a f t e r p r e l i m i n e r y
h o l d i n g f o r 8 h o u r s at 0, 7 , 27, 40, 60, 70 and 80°C f o r Ba-A
and f o r 72 h o u r s a t -12, - 5 , 0, 9 , 20, 40, 60 and 8 O o C f o r Na-X.
One sample of each k i n d of g e l was c r y s t a l l i z e d at 90° w i t h o u t
thermal p r e t r e a t m e n t . The above h o l d i n g of samples b e f o r e c r y s -
t a l l i z a t i o n e n a b l e s one t o f o l l o w t h e e f f e c t of t e m p e r a t u r e of
p r e l i m i n a r y t h e r m a l t r e a t m e n t on c r y s t a l l i z a t i o n k i n e t i c s and on
i t s f i n a l r e s u l t s . The e x p e r i m e n t s were based on t h e measurements
by means of an o p t t c a l microscope o f s i z e s of t h e l a r g e s t c r y s -
t a l s found i n t h e c r y s t a l l i z i n g g e l s at v e r i o u s p e r i o d s of t i n e
from t h e b e g i n n i n g of i s o t h e r m a l h e a t l n g o f samples. F o r Na-A
t h e edges of c u b i c c r y s t a l s were measured and f o r Ya-X - the axes
of o c t ahedre. The above measurements e n a b l e t o d e t e r m i n e g r a p h i -
c a l l y the l i n e a r r e t e o f c r y s t a l g r o w t h , t o follow i t d u r i n g t h e
whole c o u r s e of c r y e t e l l i z e t i o n p r o c e s s and t o determine t h e end
of t h e p r o c e s s ( t h e time of c r y s t a l l i z a t i o n ) by t h e d i s c o n t i n c a -
t i o r i of c r . y s t a l growth. For a l l t h e samples t h e h i s t o g r e m s were
determined which c h a r a c t e r i z e c r y s t a l s i z e d i s t r i b u t i o n i n t h e
f i n a l c r y s t a l l i z a t i o n products.
The time wher t h e growth of each mode o f c r y s t a l s s t a r t e d was
determined and t h e c u r v e s c h a r a c t e r i z i n g n u c l e a t i o n k i n e t i c s we-
r e c a l c u l a t e d from t h e s e h i s t o g r a m s and from t h e date. 0 x 1 l i n e e r
growth ret e .
289
13
10
.L
0"
20 40 60 i-;O 2,h
F i e . 1. GrowtIn i n c r y s t a l . s i z e o f t h e l a r g e s t Na-A z e l i t e c r y s -
t a l s ( 1 max ) i n c r y s t a l l i z i n g g e l s a t gOOc a f t e r thermal pre-
treatment ( t i s marked n e a r t h e c u r v e s ).
Pr
290
0.08
0.04
40 GOo 700
d
0.08 a
0.04
800 90"
n
0.08
0.04
0 61 16 t7 16 1,Y
Pig.3. Iiistograms o f t h e f i n a l c r y s t a l l i z a t i o n p r o d u c t s i n g e l
Ka-A samples a t 90°C a f t e r a p r e t r e a t m e n t at d i f f e r e n t tempera-
tures.
._ .
f r a c t i o n ) i n t h e p r o c e s s of i s o t h e r m a l c r y s t a l l i z a t i o n a t 9b.C
a f t e r pretreetment at d i f f e r e n t temperatures. The c u r v e s were
c a l c u l a t e d from t h e d a t a i n f i g . 1 and 3.
293
c o n s t r u c t e d on t h e b a s i s of d a t a i n f i g . 1 and t h e h i s t o g r a m s i n
f i g . 3 by means of r a t h e r s i m p l e c a l c u l a t i o n s . The method of con-
s t r u c t i n g such c u r v e s i s d e s c r i b e d i n /5,9/ ( s e e also / l o / and
/12/). The S-shaped curve8 i n f i g . 4 a r e well d e s c r i b e d by equa-
t i o n (11, t h e v a l u e s of k and n c o n s t a n t s v a r y i n g w i t h e a c h
p a r t i c u l a r case. These c o n s t a n t s g r a p h i c a l l y determined from
-
I n ln 11-z 1 n . t dependence e n a b l e one t o f i n d t h e p o s i t i o n of
t h e bend p o i n t o f k i n e t i c c u r v e s tinf a c c o r d i n g t o :
(2)
T h i s r e l a t i o n f o l l o w s from t h e second d e r i v a t i v e Z w i t h r e s p e c t
to t . The p o s i t i o n s and s l o p e s o f t h e c u r v e s i n f i g . 4 which
are i n t h i s c a s e determined by tinf v a l u e s one may s e e t h a t t h e
k i n e t i c s of c r y s t a l mass growth i n the p r o c e s s o f g e l s i s o t h e r m a l
c r y s t a l l i z a t i o n i s s t r o n g l y dependent on
tPr
. I n c i d e n t a l l y , as
i t i s seen from t h e d a t a i n Table 1 t h e g e l c r y s t a l l i z a t i o n time
depending on g e l p r e l i m i n a r y p r e t r e a t m e n t t e m p e r a t u r e changes
unevenly and p a s s e s a minimum c o r r e s p o n d i n g t o a temperature
tPr
c l o s e t o 4 Oo C f o r Ha-A z e o l i t e and t o 20OC f o r Wa-X z e o l i t e . As
t h e l i r - e a r rate of c r y s t a l growth is independent of t the
Pr
observed e f f e c t of t h e t e m p e r a t u r e of g e l s p r e l i m i n a r y t r e a t m e n t
on t h e d u r a t i o n of t h e i r c r y s t a l l i z a t i o n , t h e s i z e s of largest
c r y s t a l s and t h e c h a r a c t e r of c r y s t a l s i z e d i s t r i b u t i o n i n t h e
f i n a l p r o d u c t s may be account f o r o n l y under t h e c o n d i t i o r . o f non-
monotonous dependence of n u c l e a t i o n r a t e i n gels on t h e tempera-
t u r e i n t h e temperatura j i . t e r \ - r l s t u d i e d . This has been p o i n t o u t
e a r l i e r / 7 , 8 / b u t no a t t e m p t s have been made t o e s t i m a t e q u a n t i -
t i v e l y t h i s dependence. Such a n e s t i m a t i o n seems q u i t e r e a l i s t i c
t a k i n g i n t o c o n s i d e r a t i o n t h e above - mentioned independence of
c r y s t a l growth l i n e a r r a t e on t h e i r s i z e s which was also n o t e d
e a r l i e r /4,5/. I n such a c a s e t h e number of n u c l e i formed i n t h e
p r o c e s s of g e l c r y s t a l l i z a t i o n may be determined by t h e number of
c r y s t a l s i n the f i n a l c r y s t a l l i z a t i o n p r o d u c t s i f t h e volume of
a p a r t i c u l a r number o f c r y s t a l s , f o r i n s t a n c e , of 100 c r y s t a l s
i n t h e f i n a l product w a s known.
The volume of 100 c r y s t a l s ( Vlo0) may be c a l c u l a t e d from t h e
histogram according t o t h e equation:
m e t r i c a l c o e f f i c i e n t l i n k i n g d3 w i t h t h e volume Vi
The number of c r y s t a l s p e r u n i t product mass is determined
.
from :
Nf 100 / V1oop (4)
where p i s c r y s t a l d e n s i t y , t h e v a l u e s Vlo0 and Nf being
given i n Table 1. One may s e e from t h e t a b l e t h a t t h e d u r a t i o n
o f c r y s t a l l i z a t i o n ( 2 )of g e l s p r e t r e a t e d at d i f f e r e n t tempera-
t u r e s ( t ) r e g u l a r l y v a r i e s w i t h Nf which may be c l e a r l y seen
Pr
when comparing t h e r u n of curve8 1 and 2 i n fig.5.
10-8
2
6
Fig.5 .
The dependence of c r y s t a l l i z a t i o n time and of t h e o v e r a l l
number of c r y s t a l n u c l e i N growing i n g e l s from pretreatment
temperature: t h e f i g . on t h & l e f t i s f o r Na-A, on t h e right for -
Na-X.
Sinee, as it was pointed e a r l i e r , t h e number of c r y s t a l s i n
t h e f i n a l products of g e l . c r y s t a l l i z a t i o n e q u a l s t o t h e number of
t h e i r n u c l e i , t h e data i n fig.5 show t h a t t h e change i n c r y s t a l l i -
z a t i o n time r e s u l t i n g from g e l pretreatment a t d i f f e r e n t tempera-
t u r e s i s due t o temperature dependence of g e l n u c l e a t i o n r a t e i n
t h e r e g i o n studied.
The data i n fig.1 and 2 enable one t o conclude t h a t at t h e
temperature of m a x i m a l n u c l e a t i o n and a t lower temperatures down
t o O°C n u c l e a r s i z e s do not s i g n i f i c a n t l y grow. A t h i g h e r tempe-
r a t u r e s ( t ) not only f r e s h n u c l e i a r e being formed b u t a l l t h e
Pr
n u c l e i g r o w i n s i z e due t o a considerable i n c r e a s e i n c r y s t a l
growth r a t e . It is displayed i n t h e observed v e r t i c a l s h i f t s of
295
CONCLUSION
The i n v e s t i g a t i o n s i n question develop an experimental techni-
que f o r studying n u c l e a t i o n of z e o l i t e s i n a l u m i n o s i l i c a t e g e l s
and i t s temperature dependence. Study was made of t h e e f f e c t of
a l u m i n o s i l i c a t e g e l s thermal pretreatment on t h e c r y s t a l l i z a t i o n
r a t e , t h e degree of c r y s t a l d i s p e r s i o n i n Na-A and Na-X z e o l i t e s
formed and on n u c l e a t i o n i n gels.
REFERENCES
1 D.W. Breck, E.M. Flanigen, 'Molecular Sieves', SOC. Chem. Ind.,
London, 1968, pp. 47-61.
2 S.P. Zhdanov, 'Molecular Sieve Z e o l i t e s - l ' , h e r . Chem. SOC.,
Washington, 1971, pp.20-43.
3 S.P. Zhdanov, h o c . 3rd Intern. Conf. on Molecular Sieves,
Louven Univ. Press, 1973, pp.25-29.
4 S.P. Zhdanov and N.N. Samulevich, Adsorbents, t h e i r Prepara-
t ion, P r o p e r t i e s and Application, Nauka, Leningrad, 1978,
pp.10-16.
5 8.P. Zhdanov and N.N. Samulevich, Proc. 5 t h Intern. Z e o l i t e
Conf. (Ed. L.V.C. Rees) Heyden, London, 1980, pp.75-84.
6 S.P. Zhdanov, S.S. Khvoshchev and N.N. Samulevich, S y n t h e t i c
Z e o l i t e s ( i n Russian), Chimij a , USSR, 1981.
7 S.P. Zhdanov, N.N. Feoktistova, E. Jahn, Izv. &ad. Nauk Ser.
K h i m . (1986) 1720-1724.
8 N.N. Feoktistova, L.M. Vtjurina, Izv. &ad. Nauk Ser. Khim.
(1 988) 727-730.
9 S.P. Zhdanov, S.S. Khvoshchev and N.N. Feoktistova, S y n t h e t i c
296
SUMMARY
The synthesis of piperazine and triethylenediamine from ethylenediamine in ZSM-5-t e
C
P
zeolite catalysts was investigated. With strongly acidic HZSM-5, large amounts of by-pro ucts
were observed (viz., pyrazine, 2-picoline, resin-like substances and cracked products).
Reducing the strength of the acid sites by ion exchange with alkali metal cations strongly
improved the selectivities for the desired products. This effect was further enhanced by the
addition of water vapour to the feed. From the zeolites tested in this study, KZSM;5 appears
to be the best catalyst: At T = 340 "C, W/F,, = 196 gh/mol and I ~ H ~ On m: A = 12,
conversion of ethylenediamine decreased only from30 % to 80 % after more than three days
time on stream. During this time, selectivities for piperazine and triethylenediamine remained
nearly constant above 95%.
INTRODUCTION
The classical fields of industrial catalysis by zeolites comprise large volume refinery
processes, viz. catalytic cracking, hydrocracking, isomerization or dewaxing, and the
production of petrochemical commodities (e.g., ethylbenzene synthesis via the Mobil/Badger-
process or xylene isomerization) (refs. 1-3). More recently, research in catalysis focusses on
the use of zeolites for the production of more valuable products, viz. organic intermediates
and fine chemicals (refs. 4-6). For this purpose, a broad variety of zeolite structures and
compositions, and the complete set of techniques for their modification are nowadays
available. The challenge, however, is to identify products which can be manufactured with
higher selectivities, in an environmentally more acceptable manner or otherwise more
economically by using tailored zeolite catalysts.
The present paper reports on the synthesis of piperazine (PIP) and triethylenediamine
(TEDA or DABCO, 1,4-diazabicyclo[2.2.2]octane), two organic intermediates in the
production of pharmaceutical products and plastics, respectively. They are currently
manufactured commercially using non-zeolitic catalysts. Piperazine is produced by reacting an
ethanolamine/ammonia-mixture on a Raney nickel catalyst at temperatures from 150 to
298
220°C and pressures between 10 and 25 MPa. The synthesis of triethylenediamine from
ethylenediamine, diethylenetriamine or diethanolamine is catalyzed by amorphous silica-
alumina at atmospheric pressure and temperatures around 360 "C. Both processes suffer from
relatively low selectivities for the desired products. Hence, several expensive separation steps
are required downstream of the reactor (ref. 7).
In the literature, there is only scarce information on the use of zeolite catalysts for the
production of piperazine and triethylenediamine, using as feed such compounds as N-(2-
hydroxyethy1)-piperazine (ref. 8,9), ethanolamine (refs. 10,l l), ethylenediamine (ref. 11) or
diethylenetriamine (ref. 11).
In the present study, an attempt was undertaken to replace the conventional catalytic
systems by more selective zeolite-based catalysts. Among the advantages offered by zeolites
are their shape selective properties and the possibility to tailor the nature, density, strength
and distribution of their acid sites.
EXPERIMENTAL
Zeolite ZSM-5 with Si/AI=40 was synthesized from an alkali-free gel according to the
procedure outlined by Ghamami and Sand (ref.12). HZSM-5 was obtained by calcination of
the as-synthesized material for 16 hours at 540 "C in air followed by ion exchange with a In
aqueous solution of NH,CI and a further calcination at 420 "C. Li, Na, K, Rb and Cs
exchanged samples of ZSMd were prepared by dispersing the zeolite powder two times for
eight hours in a I n aqueous solution of the respective chloride salt. The zeolite powder was
pressed without any binder, crushed and sieved. The size fraction between 0.2 and 0.5 mm was
used for the catalytic experiments. They were performed in a flow-type apparatus with a fixed
bed reactor. Product analysis was achieved by on-line sampling and temperature programmed
capillary glc. Ethylenediamine (EDA), either pure or in admixture with water vapour, was
used as feed and nitrogen as carrier gas.
100
80
8?
v,
.- 60
L
0
a 40
0
W
X
20
0
0 2 4 6 8 10 12 14 16 18 20
TIME O N STREAM, h
Fig. 1. Conversion of ethylenediamine in NaZSM-5. Reaction conditions: T=340 "C,
W=O.28 g, W/F,,= 186 gh/mol, pEoA=2.1kPa, PN*U 100 kPa
strong Bronsted acid sites in this catalyst: If the interactions between these acid sites and the
basic feed or product molecules are too strong, the desorption of the products will be severely
hindered and the residence time of the basic reactants at the acid sites will be uncontrollably
high which results in the occurrence of consecutive reactions like cracking or polymerization.
To overcome the problem, two principle solutions can be envisaged: (i) the addition of an
inert component (e.g., water vapour) to the feed, which competes with the basic reactants for
the acid sites or, (ii) decreasing the interactions via a reduction of the acid strength. The latter
possibility already proved to be successful in the present case. With the aim to further increase
the selectivities to the desired products and the stability of the catalyst, additional experiments
were conducted to (i) investigate the influence of water vapour and, (ii) clarify the influence of
the strength of the acid sites by varying the alkali metal ions exchanged into ZSMJ.
Table 1 summarizes the influence of different amounts of water vapour added to
ethylenediamine in the feed stream. From these data, the conclusions can be drawn that with
increasing amounts of water in the feed (i) the selectivities for the desired products piperazine
and triethylenediamine increase, and (ii) the tendency for the formation of cracked products
decreases. Therefore, a molar ratio of 12 for H,O/EDA in the feed was used for all further
experiments.
It has been found earlier (ref. 13) that the strength of the acid sites in Z S M J zeolites can
be tailored by ion exchange with different alkali metal ions: When such catalysts are
characterized by temperature programmed desorption of ammonia (TPDA), the temperature
300
45 53 58 71
54.3 56.1 57.6 59.0
16.3 20.1 27.1 35.0
8.4 6.8 3.1 1.0
3.4 3.3 2.0 not determined
100
Li+ NCl+ K' Rb' Cs'
80
A;E - 400
0
w
v,
L
._ 60
*\ - 320 -0
4
n
0 a
< 40
- 240 t
n )i
W
0
X E
20 - 160
0
50
I I
100
I I
150
I
'
80
200
CATIONIC RADIUS, pm
Fig. 2. Activities and selectivities of ZSM-5 zeolites exchanged with different alkali metal
cations (reaction conditions: T=340 "C, W/FEDA=186 gh/mol, hH,O : ~ E D A= 12,
W = 0.28 g)
301
of maximum desorption rate decreases with increasing ionic radius of the exchanged alkali
metal cation. Hence, the strength of the acid sites decreases from LiZSM-5 to CsZSM-5.
Therefore, Lit-, K+-, Rbt- and Cs+-exchanged Z S M J zeolites were also included in the
investigations. The results are depicted in Figure 2. For the sake of clarity, only the conversion
of ethylenediamine (XED*) and the selectivities for the two major products (S,,,, bDA) are
plotted against the radius of the alkali metal cation. The data were taken after 16 hours time
on stream, when with all catalysts a nearly stable stage was reached. The catalytic activity
declines in the sequence KZSM-5 > RbZSM-5 > CsZSM-5 > NaZSM-5 > LiZSM-5.
Obviously, there is no direct relationship between the height of ethylenediamine conversion
and the strength of the acid sites as characterized by TPDA. Probably, the interactions of the
basic reactants with LiZSM-5 and NaZSM-5 are too strong to allow for a fast desorption of
the desired products. As a consequence, consecutive reactions, i. e. coke formation are
favoured. Starting from KZSMJ with its considerably weaker acid sites, there is a decline of
conversion which corresponds to the decrease of acid strength with increasing cationic radius.
With all alkali metal cation exchanged ZSM-5 zeolites, high selectivities for the desired
products (above 90%) are observed. The remaining percentage of selectivities is made up by
pyrazine, 2-picoline and cracked products.
To achieve even better selectivities and yields, conversion of ethylenediamine was varied by
varying the reaction temperature. The selectivities observed for piperazine and
triethylenediamine are presented in Figure 3. The general trend holds for all catalysts:
100 I I I I 50 I I I I
M = Lio, Nav. KA
R b o , Csc
P
80 40
x x
a a
n
a W
m I-
60 30
~ I I I I
40 20
0 20 40 60 8 0 100 0 20 40 60 80 100
’ % ’ %!
Fig. 3. Variation of selectivities for piperazine and triethylenediamine in MZSM-5 (M=Li,
Na, K, Rb, Cs) with increasing conversion of ethylenediamine. , X
( was varied by changing
the reaction temperature, all other parameters were kept constant as given in Fig. 2).
302
TABLE 2
Influence of total pressure on activity and selectivity of NaZSM-5 (T-340 "C,W =0.28g,
h 2 0: = 12).
spheric pressure, viz. with increasing conversion the selectivity for triethylenediamine
increases at the expense of piperazine. However, the sum of the selectivities never reaches the
high values attained at atmospheric pressure, i. e., far above 90 %. Surprisingly,
diethylenetriamine (DETA) was formed with selectivities between 2 and 6 %. This is in
contrast to the experiments at 100 kPa, where these high selectivities for DETA could not be
observed.
One selected catalyst, KZSM-5, was tested under atmospheric conditions with regard to its
time on stream stability in an experiment extended to 76 hours (cf. Figure 4). Over the whole
period, only a slow deactivation is observed. After about three days, conversion still amounts
to ca. 80 % with excellent selectivities to piperazine (ca. 59%) and triethylenediamine (ca.
38 %). Only small amounts of 2-picoline (S< 1%) and cracked products (S CII 2 %) are
detected. The reasons for the slow but continuous deactivation are not yet clear. There are at
least two possible explanations, viz. deactivation by coke formation or extraction of aluminum
species from lattice positions due to the hydrothermal environment (high temperature and
high concentration of water vapour). More work is underway to clarify the mechanism of
deactivation and to develop specific techniques for regeneration of the spent catalyst.
303
100 I I I I I I I I I
80 - -
x
.-
cn
L
0
n
<
w
X
0 8 16 24 32 40 48 56 64 72 80
TIME O N STREAM, h
Fig. 4. Conversion of ethylenediamine in KZSM-5; reaction conditions as in Fig. 2.
CONCLUSIONS
The synthesis of piperazine and triethylenediamine was investigated using ZSMJ-type
zeolite catalysts. Conversion of ethylenediamine over strongly acidic HZSM-5 zeolite resulted
in fast catalyst deactivation and unacceptable low selectivities for the desired products. As a
working hypothesis, this was attributed to the strong interaction of the basic reactants with the
Bronsted acid sites which results in prolonged residence times and favours consecutive
reactions. Hence two main directions were followed in order to improve the performance of
the catalyst: (i) Reducing the strength of the acid sites by ion exchanging HZSM-5 with alkali
metal cations and, (ii) adding water vapour to the feed, to make use of competitive
adsorption/desorption effects. The combined application of both measures was successful:
With KZSM-5 as catalyst and a water/feed of rh,o : tiem = 12, the sum of the selectivities
for piperazine and triethylenediamine could be increased to more than 95 % at conversions
above 80 % and with excellent time on stream stability.
ACKNOWLEDGEMENTS
Financial support by Bundesministerium fur Forschung und Technology (BMFT) of the
Federal Republic of Germany is gratefully acknowledged.
REFERENCES
1 N. Y. Chen and T. F. Degnan, Chem. En Progr., 48 (1988) 32-41.
2 N. Y. Chen, W. E. Garwood and F. G. bwyer, Shape Selective Catalysis in Industrial
A plications, Marcel Dekker, New York, 1989,303 p.
3 d Holderich and E. Gallei, Chem.-1ng.-Tech, 56 (1984) 908-915.
304
SUHHARY
By using carbon-14 labelled compounds diffusion effects in
heterogeneous catalysis can be assessed. The formation of poly-
methylated aromatics in the conversion of toluene uith methanol
on HZSH-5 zeolite catalysts is mainly a consecutive reaction, but
different diffusivities of the reactants give gaseous hydrocar-
bons, toluene and poly-methylated aromatics via a direct synthe-
sis from methanol. In xylene isomerization diffusion influences
the concentration profiles leading to wrong mechanistic reaction
mode 1 s.
INTRODUCTION
Kinetic studies only allou to drau conclusions about the rate
determining step of a reaction sequence; therefore mass transfer
to and from the external surface of the catalyst and/or mass
transfer into and out of the catalyst pores can lead to results
uhich are contrary to chemical theory. Especially in zeolite
catalysis, diffusion disguised kinetics are to be expected -
methylation of aromatics and isomerization of xylenes on HZSH-5
zeolites may serve as examples.
In methanol/toluene mixtures only a fraction of the methanol
participates in the reaction as alkylating agent, uith the re-
mainder being converted mainly to gaseous hydrocarbons (ref. 1 ) .
By using I3C(ref. 2)- or 14C(ref. 3)-labelled compounds it can
be shoun that aromatics are formed from methanol too, and the
portion of this pathuay have been assessed. Furthermore, diffu-
sion effects in medium pore size zeolites are responsible for the
violation of the validity of Broun's LFE relation ship (ref. 4)
estimating the alkylation rate of aromatics by the nature and the
number of substituents.
In xylene isomerization on medium pore size zeolites different
diffusion rates causes concentration profiles uhich are best
represented by a triangular reaction scheme (ref. 5 ) including
the unrealistic 1,3-methyl shift.
EXPERIHENTAL
For catalytic purpose, a commercial HZSH-5 zeolite catalyst
(Leuna-Uerke, GDR) uith a Si02/A1203 ratio of 56 and containing
20 X A1203 binder was crushed and sieved (0.2 - 0.4 BB). The
zeolite was highly crystalline to x-ray diffraction pattern and
according to SER pictures had a particle size in the 2 - 5 Pm
range. The quartz glass microreactor (ref. 6 ) was packed w i t h
0.25 g catalyst grains diluted uith the same amount of quartz.
Nitrogen was used as carrier gas (volume ratio 1OOO:l). 14C-
methanol and 14C-benzene ( Isocommerz 1 uero used uithout further
purification. Ring-label led 14C-toluene and 14C (7.81-para-xylene
were synthesized and checked for radiochemical purity a s uell as
for accuracy of label position (ref. 7). The reaction products
uere analyzed by radio gas chromatography using a dinonyl-
phthalate/Bentone-34 on Chromosorb U-AH-DHCS column uhich was
connected W i t h a katharometer and a proportional counter as
detectors.
" I
-4
i i I I Fig. 1.
Comparison between ob-
served (dots) and cal-
culated (line, model l )
concentration-time de-
pendence of toluene me-
thylation at 693 K uith
a ZSH-5 catalyst
\I/ methanol
[model 1)
TABLE 1
Hethylation of toluene and xylene on HZSH-5 catalyst -
Product composition (mass and activity X ) and relative molar
activities of aromatic components (toluene and xylene i n the
reaction mixture= 1.00) at 693 K, 0.1 HPa N2. 3 g/(g.h)
TABLE 2
Hethylation of a mixture of benzeneltoluene uith methanol
on HZSH-5 catalyst - Product composition (mass and activity X )
at 693 K, 0.1 HPa N2, 40 g/(g-h)
mass radioactivity
14C-methanol 14C-benzene 14C-toluene
Isomerization of xylenes
The isomeritation of xylenes has been investigated on a great
variety of catalysts. The results of earlier papers on the
homogeneously catalyzed conversion (aluminum chloride is an
example of a widely used catalyst) were consistent with a se-
quence of intramolecular 1,2-methyl shifts around the aromatic
ring (ref. 12 - 14).
1,2,4-trimethylbenzene
/+
ortho-xylene reta-xylene
it @
1 para-xylene (model 3)
\ f l \
1,2,3-trimethylbenzene 1,3,5-trimethylbenzene
Fig. 2.
Comparison between ob-
served (dots) and cal-
culated (line. model 2)
concentration-time de-
5
~-
I .5
-.+ Dendence of xvlene iso-
aerization a t 693 K
uith a ZSH-5 catalyst
l i n e ih)
ortho-xylene 7-xylene
\.para-xy 1 ene (model 4 )
Fig. 3.
Comparison between ob-
served (dots) and cal-
culated (line, model 4
and model 5 resp. 1 con-
centration-time depen-
dence of xylene isome-
0 rization at 693 K uith
I
I I
I .5 a ZSH-5 catalyst
llnc l b )
TABLE 3
Isomerization of xylenes on various catalysts - Reaction rate
constants (and 95 % confidence intervals) of model 4
meta-xylene
4-
para-xylene (model 5 )
% ortho-xylene
313
This conclusion does not mean that from the view point of
Chemical theory the isomerization of xylenes on zeolite catalysts
consists of two simultaneous reactions, but only that the contact
time dependence of the gas phase concentrations (which are the
result of CheBiCal and sorption/diffusion effects within the
catalyst particles) is well represented by a parallel reaction
network.
REFERENCES
1 N.Y. Chen, J. Catal., 114 (1988) 17
2 R. Dessau and B. La Pierre, J. Catal.. 78 (1982) 136
3 F. Bauer. R. Hanisch, U. Jockisch and Chr. Wienhold,
Chem. Techn., in press
4 H.C. Brown, J. Amer. Chem. Soc., 78 (1956) 6255
5 J.D. Collins, R. J. Hedina and B.H. Davis,
Can. J. Chem. Eng., 61 (1983) 29
6 J. Dermiettel, F. Bauer. H. Rosseler, U. Jockisch, H. Franke,
J. Klerpin and H.J. Barz, Isotopenpraxis, 12 (1976) 57
7 F.D. Kopinke, J. Dermietzel, U. Jockisch and G. Rauber,
Isotopenpraxis, 22 (1986) 388
8 R.H. Allen and I.D. Yates, J. Amer. Chem. SOC.,
83 ( 1961) 2799
9 C. Chang and A. Silvestri, J. Catal., 47 (1977) 249
10 H. B. Neimann and D. Gal, The kinetic Isotope
Hethod and its application, Acaddmia Kiado. Budapest, 1972
11 E. Dumitriu, S. Oprea and V. Hulea, Rev. Roum. Chim.,
32 ( 1987) 525
12 R.H. Allen and L.D. Yats. J. Amer. Chem. SOC.,
81 ( 1959) 5289
13 K.L. Hanson and A.J. Engel, AIChE J., 13 (1967) 260
14 H.C. Brown and H. Jungk, J. Amer. Chem. SOC., 77 (1955) 5579
15 S. Zimnieuict, H. Pilarczyk and K. Kalinski,
Chemia Stosouana, 17 (1973) 235
16 H.A. Lanewala and A.P. Bolton, J. org. Cher., 34 (1969) 3107
17 F. Bauer, J. Dermiettel, H. Rosseler and H. Koch.
Chem. Techn. , 28 ( 1976) 144
18 P. Chutoransky and F.C. Duyer, Adv. Chem. S e r . .
121 ( 1973) 540
19 J. Dermietzel, H. Rosseler. U. Jockisch, Ch. Uienhold,
H. Franke, J. Klempin and H.J. Barz. Isotopenpraxis,
14 (1978) 14
20 K.H. Robschlager and E.G. Christoffel. Can. J. Chem. Eng.,
58 ( 1980) 517
21 I. Bankos. J. Papp and D. Kallo, Acta Chim. Hung.,
119 ( 1985) 179
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors),CatQlySiSand Adsorption by Zeolites 315
01991 Elsevier Science PublishersB.V., Amsterdam
ABSTRACT
Different iron-containing H-ZSK-5 type zeolites have beenused
as catalysts for the CKHC process with n-butane as hydrocarbon
feed. Furthermore, these iron-containing zeolites have been in-
vestigated as catalysts in methanol conversion and in n-butane
pyrolysis, the two single reactions of the coupled process. The
incorporation of iron into silicon-aluminium catalysts led to an
increased lifetime, a higher hydrocarbon conversion as well as
stable olefin yields o f such samples compared to silicon-alumin-
ium-containing zeolites during the CbiHC process. Beside a lower
deposition o f coke a higher amount o f carbon dioxide was obser-
ved during the reaction. Furthermore, it was found that a partial
decoking ( u p to 70 wt.-% of deposited coke) occurs during regene-
ration by steam treatment at reaction temperatures.
I rl TH 0DUCT I0N
In the field of zeolite catalysis, the synthesis of light ole-
fins from methanol has been one of the most important subjects
for the last ten gears (e.g. refs. 1-4). Catalysts applied in this
reaction are narrow-pore zeolite types (refs. 5 , 6 ) . The short
lifetime, connected with a strong coke deposibion, is thc I ost
serious p d > o b l e : i cuch zeolite types. 23rL-5 type zeolites are
io18
described and used for the olefin production from methanol feed
as \!ell, but the olefin selectivity is lover than that of the
narrow-pore type zeolites.
Recently, metal-ion-containing zeolites (e.g. containing
gallium, chromium, vanadium and iron) with pentasil pore structure
have becn assumed to be catalysts for methanol transformation into
olefins with both high selectivity and prolonged catalyst lifetime
(e.g. refs. 7-9). Since the synthesis, characterization, and
investigation o f their catalytic performance in various reactions
(refs. 7-15) these different metal-ion-containing ZSM-5 type
zeolites have got a great influence in some catalytic reactions,
316
Catalyst synthesis
The synthesis of iron-ZSId-5 and iron-aluminium-ZSl,~-5 products
were carried out according to the method of Szostak and Thomas
(ref. 23). Fe(N0 solution o r an equimolecular mixture of
3 3
Fe(NO3I3 and A l ( N O < ) solution was acidified with H2S04 (96 :.)and
3 3
then mixed with 4.51.1 I!a,H2 2Si04. These quantities of the reactants
were chosen in order to get the required silicon-to-iron and
silicon-to-iron-to-aluminium ratios in the reaction mixture. To
the resulting gel 0.1 mol of tetrapropylammoniumbromide per mol of
Si02 was added and, after vigorous stirring, the reaction mixture
was heated in stainless-steel autoclaves at 443 1: for 24 hours
under autogeneous pressure. During thermal treatment the auto-
claves were rotating. The resulting solids were filtered, washed,
and dried.
After synthesis the organic template was destroyed by calci-
nation at ca. 823 K. The ion exchange was carried out with 0.511
NH4C1 or NH4N03 solution (each sample four times for two hours at
353 K). The ammonium-containing zeolites were calcined stepwise
from 573 K t o 823 K to get the H-form. The zeolite powder was then
treated with pure silica (65 wt.-% zeolite and 3 5 wt.-% Si02) to
form catalyst pellets. In general, three catalysts have been used
for the CPiHC investigations (sample A : silicon-to-eluminium = 22
( f o r comparison); sample B: silicon-to-aluminium = 25; sample C:
silicon-to-iron-to-aluminium = 50:l:l).
Characterization methods
The acidity of some samples was determined by the TPD of ammo-
nia. These experiments were performed by gas-chromatographic
measurement of the amount of ammonia desorbed upon heating ammo-
nia-treated samples (treated with ammonia at 393 K and followed
by desorption of physically sorbed ammonia at the same temperature
€or 30 min) at a rate of' 1 2 deg/min.
The EPR spectra of the products were recorded on a Varian E 4
spectrometer operating at X-band microwave frequency.
The X-ray powder patterns of the polycrystalline iron- or iron-
aluminium-silicate samples obtained were performed with a Guinier
equipment.
318
-I
- 7 r s I 1
Methanol-to-hydrocarbon conversion
Table 1 describes comparison between the three catalyst samples
A , E, and C during methanol conversion after two hours time on-
stream at 673 K and a WHSV o f 0.8 h-’ under atmospheric pressure.
TABLE 1
Methanol conversion and product distribution on ZSM-5 samples A ,
B and C (673 K , WHSV = 0.8 h-’, atmospheric pressure)
~ ~
Si-A1 A 92 30 35 17
Si-Pe B 97 8 58 19
Si-Fe-A1 C 93 26 33 20
t ”t ,-70
n-Butane pyrolysis
The cracking activity has been checked stepwise with the same
catalytic systems from 773 up to 953 K under atmospheric pressure
and a WHSV = 1.3 h-I. Table 2 depicts the results of pyrolysis at
773, 873 and 953 I[ on iron-ZSM-5 zeolite (silicon-to-iron = 25).
TABLE 2
Products obtained by n-butane pyrolysis using ZSM-5 sample B
-1
(silicon-to-iron = 25) as catalyst (WHSV = 1.3 h , atmospheric
pressure)
I:;
& $
0 -
u r
,
1
,
2
,
3 tlhl
from this, t i l e yliids of the wanted products were low and caused
a l o w cracking activity of these zeolite types under C L H C con-
ditions (Fig. 4b).
3 6 9 tlhl
.
N
u 3 6 9 tlhl
CON C LUS I O N S
Iron- and iron-aluminium-containing 281-5 type zeolites were
used as catalysts for the CMHC reaction as well as for single re-
actions of methanol conversion and n-butane pyrolysis. During the
CMHC reaction with the above zeolites a lower decrease in cracking
activity could be obtained together with a prolongation of the
catalyst lifetime. One reason for this fact could be due to the
324
A CKN 0W L E DG E ME N T
The authors would like to thank I r s . H.Poethke and I.Irs. U.Hahn
f o r their assistance in the experimental work and Dr. R.Liick f o r
the EPR measurements.
REFERENCES
1 S.L.Lleise1, J . P.f-;cCullough,C. H..,echthaler and P.B.Weisz,
CHEICTECH, 6(1976/2) 86
2 T.Inui and Y.Takegami, Hydrocarbon Process., (1982/11) 1 1 7
3 C.D.Chang, Catal. Rev. - Sci. Eng., 25 (1983) 1
4 Y.C.IIu, Hydrocarbon Process., (1983/5) 88
5 T.Inui, T.Ishihara, N.Eorinaga, G.Takeuchi, H.1-latsuda and
Y.Takecami, Ind. Eng. Chem. Prod. Res. Dev., 2 2 (1983) 26
6 ".Fleckenstein, K.Eelendorff and P'.Petting,
Chcri.-1nz. -Tech. , 57 (1 985/9) 800
?/ R.Szostak, V.llair and 'I'.~.Thomas,3 . Chem. SOC.,
Paraday Trans. 1 , 8 2 (1587) 487
8 T. Inui, O.Yamase, I:.Yukuda, A. Itoh, J. Tarumoto, El.lCorinaga,
T.€lagiwara and T.Takegami, Proc. VIIIth Int.Congr.Catalysis,
kestberlin, Verlag Chemie, Weinheim, 1984, Vol. 111, p. 569
9 B.Kichterlova, S. Ceran, S.Bednarova, K. Nedomova, L. Dudiltova
and P.Jiru in P.J.Grobet, W.J.Eortier, E.F.Vansaut and
G.Schulz-Ekloff (Eds.), Studies in Surface Science and
Catalysis, Llsevier, Amsterdam, 1988, Vol. 37, p. 199
10 T.Inui, Proc. IInd Symposium on C1-Chemistry Japan-GDR,
Uerlin, 1968, p. 23
11 T.Inui, A.b;iyamoto, H.Iiagata, Y.l{akino, IC.E'ukuda, II.Matsuda
and E'.Okazunii in Y.Murakami, A.Iijima and J.W.Hard (Eds.),
Proc. VIIth 1nt.Zeolite Conference, Tokyo, Kodansha (Tokyo) -
Elsevier (Amsterdam, Oxford, New York, Tokyo), 1986, p. 862
12 T. Inui, H.I#latsuda, O.Yamase, A.Nagata, K.Fukuda, T.Ultawa and
A.Miyamoto, J. Catal., 98 (1986) 491
13 P.Ratnasamy, React. Kin. Catal. Lett., 35 (1987/1-2) 219
14 S.M.Csicsery, Pure 8 Appl. Chem., 58 (1986/6) 841
15 V . P . Holderich, Pure ci Appl. Chem., 5 8 (1986/10) 1383
16 S.Nowak, B.Giinsche1, A.Martin, K.Anders and B.Liicke in
M.J.Phillips and !(.Ternan (Eds.), Proc. IXth Int.Congr.
Catalysis, Calgary, The Chemical Institute of Canada, 1988,
VOl. IV, p. 173s
17 A.Eartin, S.Nowak, B.Liicke and H.GUnsche1, Appl. Catal.
5 0 (19b9) 149
18 S.Nowak, H.Giinsche1, J.Lantzsch and K.Anders, Neftechimia,
XXVII (1987/6) 736
19 S.Nowak, Preiberger Yorschungshefte, A 761 (1987) 116
20 S.I'Jowak, Ii.Giinsche1, J.Lantzsch, B.Liicke, K.Anders, J. Jonsch,
.
11. I:ii r t ig , :I.€10 s e , I:'. R o s c he r , U Had i c k e and I<. Ilehn e r ,
DD-VP 230 545 (1983)
21 A.I,;artin,B. ~iicke,S.Nowak, H.Poethke, K.Anders, H.Giinsche1,
. . .
!I. F'ii r t ig , U Had i c ke , W H6 s e and W R o s che r ,
DD-V!P 260 060 (1987)
325
ABSTRACT
Metal phases of fine as well as coarse dispersions for Pd. Pt
or Ir are grown within a NaX matrix. The mean particle sizes
obtained under nearly identical reduction-agglomeration conditions
follow the order Pd > Pt > Ir. For comparable metal dispersions
the activities for syngas conversion or methanol formation as well
as the selectivities for methanol formation exhibit the order Pd >
Pt > Ir. A fraction of carbonaceous species deposited during
catalysis can be removed by hydrogen as methane, whereas oxygen is
needed for the conversion of the residual coke fraction to carbon
dioxide.
INTRODUCTION
It was found, that the methanol formation activities and
selectivities of Pd, Pt or Ir on silica gel follow the order Pd >
Pt > Ir [ref. 11. It was suggested that this order corresponds to
the tendency of the metal to fill its d-shell [ref. 21. Increasing
activities and selectivities for methanol formation with increas-
ing metal dispersion is reported for Pd on silica gel [ref. 31 and
Pt in faujasite X [ref. 41. A metal dispersion effect was found
for the water-gas shift reaction (WGSR) on Pt/NaX, which was ana-
logous to that one obtained for the methanol formation Iref.51.
In the following the methanol formation activities and
selectivities of faujasite X supported Pt, Pd or Ir catalysts,
exhibiting different metal dispersions, are evaluated to clarify
the different influences of metal type or metal particle size.
Additionally, the amounts of coke deposited by the reaction are
determined.
328
EXPERIMENTAL
PreDaration of the catalysts
Iron-free faujasites NaX (Si/Al ratio 1.2) were prepared by
hydrothermal crystallizations. The metals were introduced as the
ammine-ion-complexes from aqueous solutions of the chlorides
([Pt(NHa)4]2'; [Pd(NH3)4]2+; [1r(NIi3)~ClJ2*)- The loaded zeolites
were washed until chloride-free and dried at 353 K.
The autoreduction of the specimens was carried out using a
temperature program (2-3 K/min) up to temperatures between 573 and
673 K in either streaming argon or oxygen. In the case of samples
treated under oxygen the reduction was completed with hydrogen at
373 - 573 K for 1 h.
The materials investigated, the reduction treatment and the
surface average diameter, d = Inid13/Znid_Lg of the metal
crystallites are listed in Table 1. The surface average diameter
-
ds was calculated from the histograms in order to represent the
contribution of the surface more adequately. In the formula ni is
the number of crystallites within the diameter di and di+dd while
-
di = &+Ad/2. The histograms of the metal dispersions listed in
Fig. 1 were evaluated from electron micrographs. The number of
metal surface atoms/g metal was calculated from the particle size
distribution. A sphere was taken as a justifiable approximation
for the observed crystallites and the specific gravity of the bulk
metals was used. The evaluated metal surfaces were used for the
calculation of the dispersion D and the normalized activities or
turnover frequencies, respectively.
The global crystallinity of the samples was found to be
maintained even in the case of metal particles growing beyond
supercage dimensions within the zeolite matrix [ref.5].The metal
loading in atom-% was kept constant for all catalysts in order to
maintain a constant Bronsted acidity which results from the
complete reduction of the metal ions.
Catalytic measurements
The syngas conversion to methanol and methane was studied in a
continuous flow stainless steel reactor (volume: 1.6 cm3). A
fluidized bed was established by means of an external vibrator.
329
TABLE 1
Composition, reduction, surface average diameter and dispersion
D of the catalyst.
heating rates were 5 K/min, and the final temperature was 723 K.
The evolutions of methane under hydrogen and of carbon dioxide
under oxygen were monitored by infrared analyzers.
331
RESULTS
Metal disDersions
The metal phases are located inside the faujasite matrix, as
could be gleaned from the uniform distribution of the metal
particles in the specimens for electron microscopy obtained by
ultrasonic fragmentation of zeolite crystals, and as was assured
by photoelectron spectroscopy [ref. 61. The growth of particles
beyond supercage dimensions is accompanied by local zeolite
framework fragmentations and reconstructions, as evidenced by
*qSi-NMR spectra [ref. 71 and adsorption isotherm analysis [ref.
51. The recognized mesopore texture, generated in the metal phase
containing zeolite matrix, discloses that the metal particles are
surrounded by halos of free space and, thus, are fully accessible
for chemisorbing and reacting molecules.
The found surface average mean particle sizes follow the order
Pd > Pt > Ir for both types of applied reduction conditions (Table
1). The reverse order is valid for the heats of vaporization or
heats of fusion [ref. 8 1 , i.e. the energy of atom abstraction from
metal clusters. Thus, the tendency for sintering by an Ostwald
ripening mechanism should follow the order given above. Sintering
by particle migration and coalescence can be excluded for
faujasite accomodated metal phases. Only slight increases of the
mean particle sizes are observed for the used samples as compared
to the fresh ones.
Svnaas conversion
The results of the syngas conversion (cp. Table 2 ) show several
significant features. Firstly, the turnover frequencies of syngas
conversion, i.e. for the sum of methane and methanol formation,
follow.the order Pd > Pt > Ir at comparable dispersions of the
metal. Secondly, for the metals exhibiting high activities, i.e.
Pd and Pt, the turnover frequencies increase with increasing metal
dispersion. Thirdly, the metal type effect as well as the metal
dispersion effect are even more pronounced considering the
methanol activities separately. Furthermore, the increase of the
methanol selectivity with increasing metal dispersion is valid for
all metals studied here. Identical features, i.e. the metal type
effect as well as the metal dispersion effect, are observed for
the activities of carbon dioxide formation resulting from the
simultaneous WGSR. Traces of higher hydrocarbons and dimethylether
are found in the product spectrum but are not considered further.
332
TABLE 2
Turnover frequencies TOF (mole of product/gram-atom of metal
surface atoms-s),selectivities S ( T 0 F (methanol)/TOF (methane)) and
relative selectivities S r e I (selectivity of fine
dispersion/selectivity of coarse dispersion) for the syngas
conversion at H s / C O = 2.33, 573 K, 2 MPa, SV (STP) = 9375 f
75 h-1 after 250 sin time-on-stream.
The found features are valid for all reaction parameters where
the kinetic regime is preserved, i.e. where differential
conversions and sufficient distances from the thermodynamic
equilibrium of methanol formation [ref. 91 are maintained. For
instance, the metal dispersion effects become more prominent with
increasing pressure or space velocity. For the methane formation
the kinetic regime is maintained in any case, due to the
sufficient distance from equilibrium [ref. 91 under the chosen
reaction conditions. This means, that the mutual influence of the
extent of methane formation and the extent of methanol formation
can be neglected [ref. lo]. Furthermore, methanol and methane are
formed on different sites by two independent routes, presumably
[ref. 31.
The syngas conversion on fresh catalysts is always
characterized by induction periods in the beginning of the
reaction, as has repeatedly been reported previously [refs. 3, 11,
121.
PIX/O,-
PlX/Ar ----
0
U
T
- I
b
0.2
I
,--
!
PdX/O,-
PdX/Ar ----
I I
,\"
75
> 0.1-
0 -* r-' 1
- --- ----+
#
/
\
DISCUSSION
Obviously, faujasite X is a favourable support for the study of
metal dispersion effects in catalysis, since the occluded metal
particles have a low tendency for sintering, but are fully ac-
cessible to reaction mixtures. Although the relatively high Bron-
sted acidity favors the methanation selectivity in the syngas
conversion [cp. ref. 31. the found metal type effect as well as
the metal dispersion effect in the methanol formation activity and
selectivity are parallel with analogous results obtained with the
support silica gel [refs. 1.31. Strong metal-support interactions,
like formation of new phases or deposition of zeolite fragments on
the metal phase, were never observed for the applied metal/fauja-
site X system under the reduction and catalytic conversion con-
ditions used here. The observed effects can, therefore, be re-
ferred to the variations of the metal type or metal dispersion
only. It is interesting to note, that the metal dispersion effect
can surmount the metal type effect, e.g. the fine Pt dispersion is
more active in the methanol formation than the coarse Pd
dispersion (cp. Table 2).
Up to now, the effects of metal type or metal dispersion in
syngas conversion activities or selectivities are poorly
understood. Won-dissoziative chemisorption of carbon monoxide.
which might be a prerequisite for methanol formation, is found on
each of the three metals. The postulates on the participation of
Men+ surface sites in the syngas conversion [ref. 151 and the
influence of the COz/CO ratio on the density of Men+ surface sites
[ref. 161 cannot be falsified, since the methanol activities and
selectivities vary analogously to the corresponding WGSR. An
influence of the carbonaceous deposits on the catalytic effects,
as has been suggested elsewhere [ref. 41, is still uncertain,
since the fraction of carbon located on the metal surface only,
could not be evaluated separately.
335
ACKNOWLEDGEMENT
Financial support by the Deutsche Forschungsgemeinschaft is
gratefully acknowledged. We are indebted to Drs. A. Kleine and R.
Lamber for taking the electron micrographs and to Mrs. U. Melville
for carryingout the temperature programmed hydrogenation and
oxidation of the coke on the used catalysts.
REFERENCES
1 M.L. Poutsma, L.F. Elek, P.A. Ibarbia, A.P. Risch and J.A.
Rabo, J. Catal. 52 (1978) 157.
2 K. Klier, in "Catalysis of Organic Reactions" (W.P. Moser,
Ed.), Marcel Dekker, New York 1981, p.195.
3 F. Fajula, R.G. Anthony and J.H. Lunsford, J. Catal. 73 (1982)
237.
4 N.I. Jaeger, G. Schulz-Ekloff and A. Svensson, in "New
Developments in Zeolite Science Technology" (Y. Murakami, A.
Iijima and J.W. Ward, Eds.), Elsevier, Amsterdam 1986; Stud.
Surf. Sci. Catal., vol. 28, p. 923.
5 N.I. Jaeger, J. Rathousky, G. Schulz-Ekloff, A. Svensson and
A. Zukal, in "Zeolites: Facts, Figures, Future" (P.A. Jacobs
and R.A. van Santen, Eds.), Elsevier, Amsterdam 1986; Stud.
Surf. Sci. Catal., vol. 49 B, p. 1005.
6 G. Schulz-Ekloff, D. Wright and M. Grunze, Zeolites 2 (1982)
70.
7 G. Schulz-Ekloff and N.I. Jaeger, Catalysis Today 3 (1988)
459.
8 R.C. Weast, CRC Handbook of Chemistry and Physics, CRC Press,
Brea Raton 1984/85.
9 H. Landolt and R. Bbrnstein, Zahlenwerte und Funktionen
II.Bd., 4. Teil (Kalorische Zustandsgrbpen), Springer, Berlin
1961.
10 E.J. Henley and E.M. Rosen, Material and Energy Balance
Computations, Wiley, New York 1969, p. 367 ff.
11 M. Ichikawa and K. Shikakura, in "New Horizons in Catalysis"
(T. Seiyama and K. Tanabe, Eds.), Elsevier, Amsterdam 1981;
Stud. Surf. Sci. Catal., vol. 7 8, p. 925.
12 N.I. Jaeger, A. Jourdan, G. Schulz-Ekloff, A. Svensson and G.
Wildeboer, Chemistry Express 1 (1986) 697.
13 A.T. Bell, in "Structure and Reactivity of Surfaces" (C.
Morterra, A. Zecchina and G. Costa, Eds.), Elsevier, Amsterdam
1989; Stud. Surf. Sci. Catal., vol. 48, p. 91.
14 W.C. Conner, in "Hydrogen Effects in Catalysis" (Z. Paal and
P.G. Menon, Eds.), Dekker, New York 1988, p. 338.
15 E.K. Poels and V. Ponec-, Catalysis - A Specialist Periodical
Report, The Royal Society of Chemistry, London 1983, vol. 6,
p. 196; and references therein.
16 K. Klier, V. Chatikavanu, R.G. Hermann and G.W. Simmons, J.
Catal. 74 (1982) 343.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 337
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
The formation of the protonized form of acetone on HZSM-5 and
HY zeolites at room temperature has been demonstrated by high
resolution solid state NMR spectroscopy. As the reaction
temperature increases, this form undergoes gradual dimerization
folbowed by further transformations. At temperatures of about
180 C cyclization and the formation of undesorbable compounds with
polyalkylaromatic character take place. The coke formed mostly
exhibits aromatic character; the appearance of the signal at
154 ppm (TMS) indicates the presence of oxygen bonded to an
aromatic ring. The presence of either an ethereal bond or of
bonding of the phenoxy groups formed with the participation of
lattice oxygen is suggested.
INTRODUCTION
Acetone can be converted to various hydrocarbons over the acid
forms of zeolites(refs.1-3). These reactions are known to take
place via aldolization and dehydration followed by cyclization,
aromatization and cracking (refs. 4-7). Analysis of the mechanism
of these reactions in the liquid phase revealed that the
protonized form of acetone is formed in acid solutions; the enol
form is converted to diacetone alcohol (DAA). After dehydration,
this compound is then converted to mesityloxide (MO). Recent
studies have shown that a similar mechanism probably occurs in the
heterogeneously catalyzed transformations of acetone over acid
catalysts (refs. 4-6).
Various spectroscopic techniques have been employed in the
investigation of the mechanisms of catalytic reactions on solid
phase surfaces.The development of high resolution NMR techniques
for solids has also began to permit the analysis of adsorbed
complexes with low mobility on the catalyst surface (refs. 8-11).
In this study, acetone adsorbed on decationated zeolite
surfaces was studied at various temperatures by 13C HR NMR in
order to identify the surface species which could take part in the
reaction mechanism. To obtain information about the intermediate
338
EXPERIMENTAL
Materials
Decationized samples of Y and ZSM-5 zeolites differing in their
Si/Al module were used. The samples were supplied by the Research
Institute of Oil and Hydrocarbon Gases (WRUP), Czechoslovakia.
The ammonium form NH4 ,Nay-70 was decomposed in vacuum at 35OoC,
HZSM-5 zeolites with Si/Al ratio equal to 13.5 and 22.5 were
prepared from the Na parent zeolite by decationization with 0.5 M
HN03 and calcination at 550OC.
The samples for the NMR measurements were activated overnight
in a vacuum at 550OC and transferred in sealed ampouls to the
adsorption apparatus, where acetone was adsorbed in defined
quantities. The ampoules were then resealed under vacuum . They
were openeded prior to the NMR measurements under an inert
atmosphere ( N2) and transferred into the ceramic rotors for NMR
measurements.
Technique
The HR NMR spectra were measured with a BRUKER MSL-200
spectrometer equipped with magic angle spinning (MAS) technique.
As the study was carried out to investigate the adsorbed
molecules with restricted mobility at room temperature, the
spectra were measured by the cross-polarization method (CP) which
is efficient in the investigation of organic solid substances by
13C HR NMR (ref.11). This technique has a favourable effect, not
only on the signal intensity of 13C nuclei, but also on their
relaxation. It was found from the dependence of the signal
intensity of the spectrum on the contact time that the optimum
contact time for the energy transfer from H ' to I3C (under the
Hartman-Hahn conditions) was 2 - 3 ms. The rr/2 pulse for
excitation (5-6 u s ) and 0.05 s aquisition time were employed. The
number of scans required to obtain spectra with an acceptable
signal/noise ratio depended both on the adsorbed amount and on the
isotopic composition of the acetone used. For a small adsorbed
amount of acetone, 13C-enriched acetone-2-13C was employed, as
indicated in the figure captions. 13C CPMAS NMR spectra were
measured at 50.32 MHz with 20 or 25 kHz band width. The repetition
delay was 4 s , and 10 s in some cases. The ceramic rotor spinrate
339
was 4.7 - 5.0 kHz. The data obtained by IR spectroscopy and mass
spectrometry were also included in the discussion. The details of
these techniques and results are described elsewhere (ref.12).
s I 1 8 I s
300 200 100
~ . . .I .
. . . . , . ... 1 . . . . 1 . ... 1 . . . . 1 . ,
20 0 100 0 PPm
K130*8 19,8
CONCLUSIONS
The 1 3 C CPMAS NMR represents a significant contribution to the
solution of problems connected with less mobile chemisorbed
species which can participate as intermediates in the
transformation of acetone. In combination with chemical treatment
of catalysts with deposits the NMR spectroscopy can help
considerably in elucidating problems in the formation and analysis
of coke residues on zeolites.
REFERENCES
ABSTRACT
Isopropylation reaction of benzene is carried out over
large pore zeolites with characteristic structural differences
(namely La-H-Y, H-mordenite and H-ZSM-12). The activity
and deactivation pattern are correlated with structural and
acidic properties. The deactivation of La-H-Y is due to
blocking of active sites while that o f H-mordenite is due
to blocking of channels. The stable activity and selective
nature o f H-ZSM-12 for cumene can be attributed to siliceous
nature, lower acidity and presence of non-interpenetrating
channels.
INTRODUCTION
Isopropylation o f benzene using solid phosphoric acid
(SPA) catalyst and Fridel-Crafts catalysts (refs. 1-3) for
the production of cumene is an industrially important reaction.
The drawbacks suffered by these processes (environmental
and corrosion) can be overcome by using solid acid catalysts
like zeolites. Major side products formed in this reaction
are isomeric diisopropylbenzenes (DIPB) and at higher temp-
eratures n-propylbenzene (nPB). Even though the medium pore
zeolite ZSM-5 is reported (ref. 4) a s a potential catalyst
for this reaction, better stability and selectivity were
observed over large pore zeolites (ref. 5).
In view of this, isopropylation of benzene was carried
out over large pore zeolites with characteristic structural
differences, like (1) La-H-Y with cubic crystal symmetry
and three directional channel system having pore opening of
7.4 k , (2) mordenite with orthorhombic structure and unidirect-
ional dual pore system with 6.7 X 7.0 (12 MR) and 2.9 X
5.7 (8 MR) connected via side pockets of 2.9 i, ( 3 ) ZSM-
12 with monoclinic symmetry and linear non-interpenetrating
channels o f 5.7 X 6.1 "A. The stability, selectivity and
deactivation pattern were correlated with structural, acidic
348
EXPERIMENTAL
Materials
Benzene ( 99.98 X pure) and propylene (having 4 % propane)
were used for catalytic studies.
Catalysts
La-H-Y (SK-500) and H-mordenite (Zeolon 100) were procured
from M/s Union Carbide, USA and Norton, USA, respectively.
ZSM-12 was prepared in this laboratory following the procedure
reported (ref. 6 ) earlier in the literature. Co-crystallis-
ation of zeolite beta was avoided.
Characterisation
Crystalline phase purity and the state of aluminium in
the framework of these samples were characterised by the
techniques like XRD, IR and MASNMR spectroscopy. Acidity
of the samples was measured by the irreversibly adsorbed
ammonia. Adsorption studies were carried out at 25°C and
P/Po = 0.5 using a McBain balance with silica spring of
sensitivity of 4' 50.0 cm gm-'.
Catalytic reactions
The catalyst was pressed and crushed into 10-20 mesh binder
free self supported pellets. Prior to catalytic runs, the
catalyst was activated in a flow of dry air at 45OOC for 8
hrs. Catalytic runs were carried out in an integral, fixed
bed, down flow, silica reactor at atmospheric pressure.
Benzene was fed by a syringe pump (Sage Instruments, USA)
while propylene was metered through a mass-flow controller
(Matheson, USA). The products were analysed by gas-chromato-
graphy (Shimadzu, Model 15A) using Apiezone L column for
liquids and Poropak Q column for gaseous samples.
Influence of temperature
In Table 3 the results on the influence of temperature
on the product distribution over H-ZSM-12 are p r e s e n t e d .
At temperatures below 200°C, the conversion of p r o p y l e n e i s
not completed. With t h e i n c r e a s e of temperature, a continuous
350
TABLE 2
I s o p r o p y l a t i o n o f benzene o v e r z e o l i t e c a t a l y s t s
R e a c t i o n t e m p e r a t u r e = 230OC; P r e s s u r e = Atmospheric;-TOS = 3 h r s ;
Benzene t o p r o p y l e n e molar r a t i o = 6 . 5 ; WHSV = 2 . 5 h r
Product d i s t r i b u t i o n (wt % )
Aliphatics 0.74 0.06 0.30
Benzene 77.10 77.80 78.30
T o l u e n e t C8 a r o m a t i c s 0.97 0.04 0.27
Cumene 18.52 20.50 18.10
nPB 0.40 0.02 0.74
C9-C11 a r o m a t i c s 0.29 0.04 0.12
DIPB 1.75 1.55 1.78
H.B.F 0.18 0.01 0.26
1./F
t,
w
h 19 a H.ZSM-I2
* H MORDENITE
rLa H Y
2 4 6
F i g . 1 . C a t a l y t i c p e r f o r m a n c e o f t h e wide p o r e z e o l i t e s i n t h e
i s o p r o p y l a t i o n of b e n z e n e w i t h t i m e o n s t r e a m (TOS).
R e a c t i o n temp. = 230OC; WHSV = 2 . 5 h r - 1 ;
Benzene t o p r o p y l e n e m o l a r r a t i o = 6 . 5 .
351
TABLE 3
Influence of temperature on product distribution
Catalyst = H-ZSM-12; Benzene to propylene molar ratio = 6.8;
WHSV = 2.5 hr-1
> 100-
t
>
F 95-
_-
-
0
w
d 90.
xCUMENE*UPB
CUMENE
v)
s 85-
5 10 IS 20
MOLE RATIO
100 .
'
95
t
CUMENE *DIP6
t .
1 . CUMENE
:\
90
c
;
0
85.
fn
s 80
1 2 3 4 5 6 7
SPACE VELOCITY ( W H S V I h i l
Thus the
optimised condition for propylation of benzene
over H-ZSM-12 catalyst are at temperature 230°C, WHSV, 2.5
hr-l, and reactant mole ratio, 6-8.
As already mentioned, the ageing studies indicated faster
deactivation o f La-H-Y and H-mordenite catalysts. Whereas
H-ZSM-12 catalyst did not deactivate even after 200 hrs of
time on stream (TOS), therefore faster deacpivation was carried
out by accelarated ageing. All the three coked samples were
subjected to thermal and sorption studies to find out the
probable cause of deactivation. Fig. 4 presents the cumene
sorption kinetics on fresh and coked samples.
r I
CATALYST Lo H Y
o FRSH SAhlPLE
DEACTIVATED
SAMPLE 1
0
V , 6
n
I= -=+/
a
t
I
w
2
w l4
5u 10 f
2 r
5t
= I
10 20 30 ' 120
TIME ( min 1
TABLE 4
Physico-chemical studies on fresh and coked catalyst samples
CONCLUSIONS
H-ZSM-12 is a superior and selective catalyst in the
alkylation of benzene with propylene.
The catalytic activity and stability are dependent on the
acidic and structural properties.
Coking of La-H-Y is due to acid site blocking, in
H-mordenite, it is due to channel blocking while deactivation
of H-ZSM-12 required accelarated ageing.
ACKNOWLEDGEMENT
We sincerely thank Dr. P. Ratnasamy, for his constant
encouragement throughout this investigation. We also thank
Dr. V.G. Gunjikar and Mr. S . P . Mirajkar, for helping in
356
REFERENCES
Y.C. Y e n , S t a n f o r d Res. I n s t . E c o n . R e p . , 22 A ( 1 9 7 2 )
and 22 B (1973).
2 I b i d , 49 (1969)
3 E.S. M o r t i k o v , S.R. Mirzabekova, A.G. Pogorelov, N.F.
Konov, R . F . M e r h a n o v a , A.Z. D o r o g o c h i n s k i i a n d Kh. M .
M i n a c h e v , N a f t e k h i m i y a , 16 ( 1 9 8 8 ) 7 0 1 .
4 W . W . K e a d i n g a n d R.F. H o l l a n d , J . C a t a l . , 109 ( 1 9 8 8 ) 212.
5 B.S. Rao, I. B a l a k r i s h n a n , V.R. Chumbhale, A . R . Pradhan
and P. Ratnasamy, P a p e r p r e s e n t e d a t F r i s t Tokyo C o n f e r e n c e
o n A d v a n c e d C a t a l y t i c S c i e n c e a n d T e c h n o l o g y (TOCAT l ) ,
J u l y 1-5, 1990.
6 E . J . R o s i n s k i a n d M . K . R u b i n , U.S. P a t e n t 3 , 8 3 2 , 4 4 9 ( 1 9 7 4 ) .
7 D . A . B e s t a n d B.W. W o j c i c h o w s k i , J . C a t a l . , 4 7 ( 1 9 7 7 ) 11.
8 H.G. Karge and E.P. Boldingh, Catalysis Today, 3
( 1 9 8 8 ) 53.
9 P.B. V e n u t o a n d P . S . L a n d i s , Adv. C a t a l . , 18 ( 1 9 6 8 ) 2 5 9 .
10 P.E. E b e r l y J r . a n d C.N. K i m b e r l i n J r . , I n d . Eng. Chem.
P r o d . Res. D e v . , 9 ( 1 9 7 0 ) 335.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 357
0 1991 Elsevier Science PublishersB.V., Amsterdam
R.W.
E.S. S H P I R O ~ , ~ 2 G . J . T U L ~ O V A ' . A.V. PFEOBR~IENSKY'.
JOYNER~,
O.P. TKACHENKO , T.V. VASINA , O.V. BRAGIN and Kh.M. MINACHEV
'N.D.Zelinsky Institute of Organic Chemistry, USSR Academy of Sciences, Moscow,
YSSR
The Leverhulme Centre for Innovative Catalysis, The University of Liverpool,
Liverpool, England
SUMMARY
Pt-Cr/H-ZSM-S samples were characterized by EXAFS and XPS and their catalytic
activity in ethane and methane aromatization was examined. EXAFS shows clear
evidence of Pt-Cr alloy particles formation in samples reduced at 823 K. Most of
these particles is located within zeolite structure and coordinated to zeolitic
oxygen. The changes of catalytic activity in C1-C3 alkane aromatization and
hydrogenolysis caused by chromium are related to alloying effect.
INTRODUCTION
It is well known that VIII Group metal additives play an important role in
catalysis of lower alkanes aromatization which proceeds on modified high-silica
zeolites (refs. 1-4). Among other metals platinum behavior is established rather
in details and such characteristics as dispersion and electronic state was shown
to be key factors for high catalytic performance in ethane and propane aromati-
zation (refs. 4-6). Recent EXAFS studies (ref. 7 ) proved earlier suggestion that
platinum clusters are located within zeolite structure in the proximate vicinity
t o Bronsted acidic centers and they are most probable candidates for active si-
tes in alkane dehydrogenation step (refs. 5-71. Platinum might play even greater
role in methane aromatization. This reaction was discovered (ref. 8 ) to proceed
over modified pentasils at 1023 K to yield up to 4-14% of aromatics.
In connection with aromatization reactions two features of platinum loaded H-
pentasils became important: (a) stabilization of very dispersed Pt particles at
temperatures as high as 823-1023 K; (b) reducing Pt hydrogenolysis activity and
as consequence coke formation and catalyst deactivation. To maintain these cha-
racteristics of platinum in reforming catalysis promotion by second metal (Re,
Sn, In, Ga, Cr) is widely used, chromium is definitely suppressed platinum acti-
vity in hydrogenolysis (refs. 9,101. Our previous studies (ref. 6 ) also sugges-
ted the strong influence of chromium on platinum behavior in ethane hydrogenoly-
358
EXPERIMENTAL
Catalyst containing 0.5 wt % Pt and different contents of chromium (0.13,
0.75 and 1.25 wt % I were prepared by simultaneous impregnation of H-ZSM-5 (Si/A1
= 16.5) with a mixture of H PtC16 and (CrO 1 solutions, 0.5% Cr/H-ZSM-5 was ob-
2 3 x
tained by impregnation with (CrO 1 and 0.75% Pt/H-ZSM-5 was prepared by ionic
3 x
exchange of [Pt(NH3l41Cl2 with NH -EM-5 (ref. 4). Samples were calcined in an
4
air at 623 K for 2 h and subsequently at 790 K for 3 h.
EXAFS measurements were performed at the Daresbury synchrotron radiation SQU-
rce and reduction of the catalyst specimen was carried out in-situ at 1 bar in
flowing hydrogen at 623 and 823 K. Data were collected for the Pt L I11 edge and
analyzed by standard methods (ref. 11). XPS analysis of the Pt-Cr/H-ZSM-5 has
been performed after in-situ reduction in 1 bar of flowing hydrogen at 823-873 K
in a specially developed cell attached directly to Kratos XSAM 800 spectrometer
and using Mg K radiation. The analysis of Pt-Cr/H-ZSM-5 samples after methane
a
aromatization reaction was performed with Kratos ES 200B spectrometer according
procedure described in (refs. 4 , 6 ) . Pt 4f + A 1 2p and Cr 2p peaks were analyzed
by using peak synthesis programme with PDP 11/03L computer. The details of peak
synthesis treatment for these particular spectra are described in (ref. 12).
Ethane and methane aromatization were tested in microcatalytic pulse reactor
in He flow at 823 K and 1023 K respectively. Propane and ethane hydrogenolysis
were performed in flow reactor at hydrocarbon/H2 ratio equal to 1/10 in diffe-
rential mode (hydrocarbon conversion does not exceed 5-7%).
particles remain to be located inside zeolite matrix (ref. 7). The particular
0
features of 7-13 A particles are 1-4% contraction of nearest Pt-Pt distance with
respect to the bulk and bonding between metal and oxygen of zeolitic framework.
XPS positive shifts of Pt 4f level observed for such particles have been inter-
preted in terms of charge transfer from metal to zeolite (refs. 4-6).
Fig.1 and Table 1 shown that main structure characteristics of Pt particles
remained eventually the same after promotion of 0.5% Pt/H-ZSM-5 with chromium
0.03 1
kX(k)/k b I
0.08 Fig. 1. Pt L I 1 1 EXAFS
for the Pt-Cr/H-
0.04 ZSM-5 catalyst
reduced at 623 K
(a) and 823 K
0.00 (b), solid line -
experiment;
0.04 dashed line -
calculated using
the parameters
0.08 given in Table 1.
0.12
360
(0.75%) and reduction at 623 K. The average coordination number for the first
0
Pt-Pt shell is equal to 5 and Pt-Pt distance is of 0.08 A shorter than for Pt-
foil. Pt-0 distance with C.N. 1.4 is also contributed to EXAFS spectrum. The
comparison of these data with those obtained for 0.5% Pt/H-ZSM-5 calcined at the
same temperature (793 K) (refs. 6,7)indicated some stabilization effect caused
by chromium.
TABLE 1
Best fit Pt L I 1 1 edge EXAFS data for 0.5% Pt-0.75% Cr/H-ZSM-5
~~
TABLE 2
XPS analysis of 0.5% Pt-0.75% Cr/H-ZSM-5
fresh 0.44a)
B.E..eV 74.0 - 577.5 579.5
% 100 74.8 25.2
air,793 K 0.033
B.E. ,eV 72.3 73.9 - 577.0 580.8
x 44.3 55.7 78.8 21.2
H2,823 K 0.032
B.E. ,eV 72.3 - 573.4 577.2 -
% 100 12.3 87.7
02,298K 0.037
B.E.,eV 72.8 577.2
x 100 100
H2,873 K 0.029
B.E. ,eV 72.2 - 573.0 577.4
% 100 16.2 83.8
a) Cr/Sibulk = 0.009
crease of Cr/Si ratio which can reflect migration of part of Cr ions into the
channels. At 623 K in hydrogen only Cr(II1) was found but increase of reduction
temperature up to 823 K gives rise new doublet in Cr 2p envelope which is
characteristic of Cr(0) (refs. 6.12). The degree of Cr(0) reduction reached to
10-15% at 823-873 K.
One of the explanation of the observed difference is that zeolite could cont-
ribute to hydrogenolysis (dehydrogenation) or cracking of alkanes at higher tem-
peratures. This explanation is rather speculative because nor H-ZSM-5 neither
0.75% Cr/H-ZSM-5 shown no noticeable activity in C2H6 or C3H8 hydrogenolysis in
the temperature range studied. But we could not ruled out possible dual-
functional behavior of Pt-Cr/H-ZSM-S. Despite of complications connected with
possible zeolite-catalyzed reactions it is obvious that chromium suppressed in-
trinstic hydrogenolysis activity of platinum. This is particularly confirmed by
the fact that 0.5% Pt-0.75% Cr/H-ZSM-5 reduced at 623 K, when no metallic Cr is
formed, has the same activity as Pt/H-ZSM-5.
TABLE 3
Hydrogenolysis activities of Pt- and Pr-Cr/H-ZSM-S
1 2
T = 1023 K
g = 500 mg cat.
2 0 0 ,
5 10 15 Number of cH4 pulees
Fig.2. The dependence of aromatics (B+T) yield on CH4 pulse number: 1 - 0.5%
Pt-0.75% Cr; 2 - 0.5% Pt-0.75% Cr (was studied by P S I ; 3 - 0 . 5 %
Pt-1.3% Cr; 4 - 0 . 5 % Pt-0.13%Cr; 5 - 0.5% Pt; 6 - 0.75% Cr.
Post-reaction studies
The enhancement of methane aromatization activity with Pt-Cr sample seems to
be indicative of platinum-chromium interaction rather than simple additive
effect. This interaction may appear in the course of the reaction which proceeds
at high temperature and i n purely reducing atmosphere. To verify this assumption
XPS spectra were monitored after treatment of 0 . 5 % Pt-0.75% Cr/H-ZSM-5 with He
and with 1, 3, 10 and 17 pulses of methane at 1023 K (Table 4). As was expected
(refs. 4-7) platinum was part,?lly reduced even during air calcination and its
reduction was progressing in He at 1023 K. After interaction with methane extent
of Pt reduction increased but about 1 5 2 0 % of Pt gives spectrum with higher B.E.
than for pure metal. By analogy with Pt/H-ZSM-5 treated with hydrogen or ethane
this spectrum can be assign to Pt" clusters. The lack of significant change of
364
TABLE 4
XPS analysis of 0 . 5 % Pt-0.75% Cr/H-ZSM-5 after methane aromatization
a) P
t
'
+ ; b) a few Cr(Ol was found from peak synthesis
CONCLUSION
Let us discuss in conclusion some points concerning local structure of Pt-Cr
zeolites and its possible effect on catalysis. Both EXAFS and XPS data clearly
demonstrated that Cr(0) is formed during H2 treatment at 823-873 K part of which
is alloyed with platinum. Other properties of Pt particles such as dispersion,
location, crystallographic structure are rather similar to those in Pt/H-ZSM-5
(ref. 7). Thus we can neglect size effect and discuss the data in terms of Cr
promotion or poisoning. Chromium in H-ZSM-5 is present in several forms : (a)
365
Pt-Cr alloy; (b) separate Cr(0); (c) Cr(II1) ions in channels; (d) chromia on
external surface. Higher XPS Cr(O)/Pt(O) ratios with respect to found from EXAFS
suggest that a part of chromium exist in separate phase, although there is no
indications from TEM o r XANES that big Cr(0) particles are formed. In addition
about 90% of total chromium content is not reduced and it can be located or in
the channels either on external surface. The latter is more probable when we
take into account higher Cr/Si ratios on the surface.
Size and composition of the alloy particles may be deduced from EXAFS
results. The sum of Pt-Pt and Pt-Cr nearest neighbor coordination number is 6.2,
very close to that found in 13-atom clusters which is 6 . 5 . For other samples
even less chromium is included into Pt-Cr particles (ref. 14) although chromium
content in bulk alloys can reach to 71% (ref. 15). We can therefore assume that
in diluted alloys chromium is homogeneously distributed over the particle. The
limit of chromium concentration in alloy can be explained by the fact that only
a part of chromium i s within zeolite structure. Also, Pt particles which size is
limited by channel cross-section can dissolve only a limited number of chromium
atoms. Besides, the surface of platinum particles can be decorated by chromia.
Thus, the difference in catalytic behavior of Pt/H-ZSM-5 and Pt-Cr/H-ZSM-5 is
likely to be due to platinum-chromium interaction in small platinum-chromium
particles and not so well-defined interaction between Pt particles and Cr20g. In
agreement with data (ref. 10) we ascribe the suppression of hydrogenolysis acti-
vity to alloying of Pt-Cr. The ensemble model can be proposed as simplest one to
explain, for instance, stronger poisoning of propane hydrogenolysis than ethane
one for sample 0.5% Pt-0.75% Cr/H-ZSM-5. But stronger drop of ethane hydrogeno-
lysis activity on 0.5-1.25% Cr requires more complex model. It should taken into
account platinum-chromium electronic interaction, strong hydrocarbon adsorption
on Cr sites and so on. Pt and Cr lie on opposite sides of their respective vol-
cano curves for alkane hydrogenolysis (ref. 16). Hydrocarbons are insufficiently
strongly adsorbed on Pt while adsorption is too strong on chromium for optimal
activity. This can inhibit hydrogenolysis which proceeds at relatively low tem-
peratures and on pure metallic surface (low conversions) but at the aromatiza-
tion conditions (high temperatures, coking) the situation may change in such way
that stronger hydrocarbon adsorption on Pt-Cr would play a positive role. This
is especially important for methane which activated very hardly. Taken into
account mechanism of methane oxidative coupling and thermodynamic hindrances of
direct methane aromatization (refs. 8,171 one can expect that first stage of me-
thane activation must be oxidative one and zeolite or oxide oxygen can partici-
pate in initializing reaction. But even in pulse mode the methane aromatization
does not look as simple stoichiometric reaction and it definitely involves cata-
lytic steps. For this particular system the presence of Cr203as source of mobi-
366
le oxygen is not enough to provide high activity. In contrast, the system Pt-
Cr/Cr 0 /H-ZSM-5 gives rise to maximum effect. The Cr reduction by reaction mlx-
23
ture was recently found for 0.5% Pt-1.25% Cr/H-ZSM-5. Similar activity of three
Pt-Cr samples in methane aromatlzation 1s in accordance with EXAFS data lndlca-
tlng formation Pt-Cr alloys of close composition in samples with very different
total Cr/Pt ratios (ref. 14).
REFERENCES
O.V. Bragln, T.V. Vasina, Ya.1. Isakov, N.V. Pallshklna, A.V.Preobrazhensky,
B.K. Nefedov and Kh.M. Mlnachev, Stud. Surf. Scl. Catal., 18 (1984) 31-36.
C.W.R. Engelen, J.P. Wolthulzen, J.H.C. van Hoof, H.W. Zundbergen. Proc. 7th
Int. Zeolite Conf., 1986, pp.709-716.
T. Inul, J.Maklno, F. Maganos, A. Mlymoto. Ind. Eng. Chem. Res. and
Develop., 26 (1987)647-652.
O.V. Bragln, E.S. Shplro. A.V. Preobrazhensky. S.A. Isaev. T.V. Vasina,
B.B. Dysenbina, G.V. Antoshin and Kh.M. Mlnachev, Appl.Catal., 27 (1986)
219- 231.
Kh.M. Mlnachev and E.S. Shpiro, React. Klnet. Catal. Lett., 35 (1987) 195-
206.
E.S. Shplro, G.J. Tuleuova, V.A. Zalkovskii, O.P. Tkachenko. T.V. Vasina,O.V.
Bragin and Kh.M. Minachev, in H.G. Karge and J. Weitkamp (Eds.), Zeolites as
Catalysts, Sorbents and Detergent Builders, Elsevier, Amsterdam, 1989, pp.
143-152.
E.S. Shplro, R.W. Joyner, Kh.M. Minachev and P.D.A. Pudney, J. Catal., to be
published
O.V. Bragin, T.V. Vaslna, A.V. Preobrazhensky and Kh.M. Minachev, Izv. AN
SSSR, Ser. Khlm., 1989, pp. 750-751.
K. Anders, R . Feldhaus, H.-G. Vieweg, S. Engels, H. Lausch et al., Chem.
Tech.(Lelpzlg) 37 (1985) 65.
10 S . Engels, H. Lausch, B. Peplinski, M. Wilde, W. Morke, P. Kraak, Appl.
Catal., 55 (1989)93-107.
11 S.J. Gurman, N. Blnstead, I . Ross, J. Phys. C (Solid State Phys.), 17 (1984)
143.
12 W. Grunert, E.S. Shpiro, R Feldhaus, K. Anders, G.V. Antoshln and Kh.M.
Minachev, J. Catal.,100 (1986) 138-148.
13 R.W. Joyner, K.J. Martln and P. Meehan, J. Phys. C (Solid State Phys.), 20
(1987)4005.
14 E.S. Shpiro, R.U. Joyner , unpublished results
15 M. Hansen, Constitution of Binary Alloys, 2nd edn. (Mc Graw-Hl11, New
York,1958).
16 J.H. Sinfelt, Catal. Revs. Scl. Eng., 3 (1970) 175-205.
17 Kh.M. Mlnachev, N.Ya. Usachev, V.N. Udut and Yu.S. Khodakov, Russian Chemical
Reviews, 57 (1988)385-404.
G . Ohlmann eta!. (Editors), Catalysis and Adsorption by Zeolites 367
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
Methane splitting was studied over nickel containing Na-ZSM-5 catalysts and at a Ni/AI,O,
catalyst for comparison The reaction took place between 673 and 1073 K The highest activity
was found between 923 and 1023 K The ZSM-5 catalyst showed the best long time behaviour
Good working conditions were only obtained in fluid bed realized by a vibration reactor. In
the temperature region between 673 and 973 K a rate equation containing a first order term
with respect to methane and a reversible second order one concerrung hydrogen best fulfilled
the experimental results
INTRODUCTION
The formation of carbon filaments (or whiskers) as a result of the decomposition of hy-
drocarbons on metal surfaces or, respectively. catalysts containing Fe. Ni or Co particles has
been known for a long time 11-31, Since this time the practical interest has been mainly di-
rected on the question how to avoid the whisker growth because it is an important reason
for the formation of carbon deposits on reactor walls and for mechanical break-down of ca-
talyst particles.
A good review about the production of filamentous carbon is given by BAKER [ 4 :I who
emphasizes that the scientific interest should be drrected not only on the prevention of car-
bon-filament formation but also on the possibilities to produce such materials for useful aims,
thus for electrodes with high surface area and electrical conductivity, for new generations of
3-D composites 141,for carbon fibres [ 5 ] and possibly as materials for adsorption processes.
As could be shown by electron microscopy the whisker consists of a tubular filament
with a co-axial channel [ 6 ] and a metal particle at the growing end of the filament. The
whisker structure is graphitic [7,81 with the basal planes parallel to the whisker axis. The
core of the whisker may be void or filled with carbon material of lower density.
It could be shown that after an induction period which is necessary for saturation of the
nickel particle with carbon the single whisker grows after a rate equation of zero order 191.
Moreover the rate of growth depends on the reciprocal root of the dlameter of the particle.
The growth can be inhibited when the leadmg face is encapsulated b y a layer of amorphous
carbon.
Whereas the whisker growth is obviously determined by the diffusion of carbon through the
metal particle leading to a concentration gradient in the metal there are different interpreta-
368
EXPERIMENTAL
Preparation of catalysts
Pellets of catalyst material consisting of 70 mass per cent of Na-ZSM-5 zeolite and of 30
mass per cent of y-A1203 were impregnated with such amounts of solutions of nickel nitrate
that the nickel content of the dry material was 20, 10 and, respectively, 5 mass per cent.
After heating in dry air for about 3 hours at 773 K the pellets were broken up and classified
to a fraction of 0.2 _..0.4 mm.
Catalvtic measureme&
For catalytic measurements a vibration reactor was used. It consists of a quartz tube
with an inner diameter of 1 cm which is elastically suspended from springs. By means of a
magnetic oscillation apparatus the reactor can vibrate with an amplitude of about 0.5 cm
and a frequency between I and 50 Hz. usually at I5 Hz.
The flow rate is controlled by a Brooks flow controller and measured at the reactor out-
let. The gaseous reaction products are analyzed by GC using a 2 m PORAPAK T column.
Catalytic experiments were carried out using 0.1 ... I g of catalyst. The catalyst was he-
ated in a stream of dry He up to 773 K and kept at this temperature for 3 hours. then cooled
down to 473 K, newly heated in a stream of hydrogen up to 673 K and reduced at this tem-
perature for 3 ... 4 hours. After having switched the gas stream to pure methane the vibrati-
on of the reactor was started and the sample was heated with a rate of 10 K per min up to
the reaction temperature.
369
Tpr emeriments
In order to find out the optimum reduction conditions samples of the catalysts were re-
duced in a tpr apparatus consisting of a quartz reactor, a furnace controlled electronically
and a heat conductivity cell. The reducing gas mixture was argon containing 5 per cent of
hydrogen. The heating rate could be chosen between I and 20 K p e r min and was usually
10 K per min.
Evaluation of the experiments
It was assumed that because of the mechanical vibration of the reactor and of a relati-
vely high flow rate a fluid bed reactor was approached which can be kinetically described
by the model of a perfectly mixed reactor. For kinetic evaluation it must be considered that
the
-
CH, C 2 H, +
reaction is connected with a change of the mole number. In order to count the degree of
conversion X first of all the molar fractions xcH4and xH2were determined by GC.
Then the conversion degree could be expressed as
a SVCHddt (3)
For the kinetics of methane splitting a rate equation of the following form was assumed:
370
In case of the perfectly mixed flow reactor the rate I results from
The partial pressures of methane and hydrogen can be written in the following manner con-
sidering the change of the mole number during reaction ( p - total pressure):
From equ (7) k , and Kp can easily be calculated by regression and from the rate and
equilibrium constants the activation energy EA1 and the heat of reaction ARH can be deter-
mined using the equations of Arrhenius and van t Hoff
uniform process as can be seen from the only less structured peak'with the maximum at about
690 K. Taking into account that the peak-maximum temperature decreases when the heating
rate is diminished it can be concluded that a reduction temperature of about '100 K should be
Fig. 1. Tpr spectrum of a 0.2 NiNa-ZSM-5 zeolite (heating rate 10 K per min)
sufficient. Indeed, a reduction degree of about 80 per cent could be calculated from the peak
area related to the whole amount of nickel. The measured peak-maximum temperature is in
good agreement with results of other authors who studied the reduction of NiO species [ 121.
Considering the activity of the various catalysts it can be stated that over nickel fauja-
sites only a very low amount of carbon was formed until the reaction broke down by rapid
deactivation (at 1 g of 0.45 NiNaX only 0.13 g of carbon were formed. the same amount of
0.5 NiNaY led to 0.2 g of carbon).
Na-ZSM-5 catalysts containing 5 or. respectively. 10 mass per cent of nickel showed lo-
wer activity and more rapid deactivation compared to catalysts with 2 0 per cent of nickel.
Comparison of the activity and long-time behaviour of convenient Ni/AI2O3 hydroge-
nation catalysts containing about 50 per cent of nickel with that of 0.2 NiNa-ZSM-5 catalysts
was of special interest: Whereas the catalytic activity of the N i l A1,0, catalyst is comparable
to that of the 0.2 NiNa-ZSM-5 its long-time behaviour is much worse.
Thus in an experiment with 0.2 NiNa-ZSM-5 after 7 hours of time on stream the fourfold
amount by weight of carbon related to the weight of catalyst was formed but the degree of
conversion diminished only from 0.6 to 0.4 whereas the Ni/AI,O, catalyst produced only
twice of its own weight until it deactivated dramatically.
In fig. 3 the momentary methane consumption at constant inlet flow rate of methane is
shown in dependence on temperature for the 0.2 NiNa-ZSM-5 catalyst. Catalytic activity can be
observed between 673 and 1073 K with a maximum in the 1000 . . . 1030 K region.
Similar behaviour was found by other workers [6 1 which used Ni / MgU catalysts. The loss
of activity at temperatures higher than loo0 K should not be due to deactivation by carbon
deposition but by adsorption effects in a rate determining surface reaction [ 13 1. The results
obtained in this work for the Ni-ZSM-5 and Nil A1,0, catalysts are contrary to this explanation
because almost no catalytic activity was observed at temperatures beolw 1000 K when the
catalyst had worked before at temperatures over 1100 K (in the temperature region where the
reaction rate is decreasing) indicating a poisoning of the active nickel centres by deposition
of amorphous carbon. In fig. 2 the conversion is shown in dependence on time on stream. As
can be seen the conversion degree decreases in the course of 7 hours only from 0.6 to 0.4.
When carrying out the same experiment without vibration of the reactor the activity dramati-
cally decreases after short reaction times because of sticking together of the catalyst pellets.
Kinetic studies were carried out in a temperature region between 673 and 923 K. In contrast
to other authors 1141 an inhibition by hydrogen was not observed, thus a rate equation ex-
pressing the conditions for the equilibrium reaction CH, - C + 2H2 could be used (equ. (4)).
In case of the 0.2 NiNa-ZSM-5 catalyst the activation energy of the splitting was (1 13 2.2) kJ
per mole, the reaction heat ( 1 24 : I . 2 ) kJ per mole. For the Ni/A1203 catalyst a n activation
energy of ( 1 10 : 1.4) k] per mole and a heat of reaction of ( I 25.4 1.2) kJ per mole could
be calculated. These values are in good agreement with results of other authors r 151.
In figs. 4 and 5 Arrhenius and van? Hoff plots are shown for the 0.2 NiNa-ZSM-5 catalyst.
In Tab. 1 the equilibrium constants calculated from the experiments or, respectively. from
thermodynamic data are listed together with the respective equilibrium degrees of conversion.
TABLE I
Equilibrium constants and equilibrium degrees of conversion in dependence on temperature
T[Kl Kplbarl x-
theor. 0.2 NiNa-ZSM-5 Ni/AI,O, theor. 0.2 NiNa-ZSM-5
~
Ni/A1203
873 2.1 I .34 0.921 0.59 0.50 0.4 3
923 3.92 3.44 2.35 0.70 0.6 8 0.6 1
973 7.32 7.89 5.43 0.8 I 0.8 2 0.76
1023 12.35 16.70 11.6 0.8 7 0.90 0.86
1073 20.7 33.0 2 3.0 0.9 2 0.94 0.9 2
The results show that the equilibrium conversion can be higher than the value calculated
from the theoretical thermodynamic data, especially in the upper temperature region. This
can be explained by the fact that the gas phase does not contact with the pure graphitic
carbon surface but with a carbidic one at the exposed surface of the nickel partic!e (e.g.
Ni3C ).
374
. _..._ _
1 ..... . . -..
'\
... . _..-.
C
b? -1
+
r;
-2 '4,
\
'
\.
-3 ,Q\,\
-4 '\
1
1.6
375
CONCLUSIONS
The splitting of methane can be well realized on nickel containing Na-ZSM-5 zeolites.
When using a vibration reactor which allows fluid bed condtions a quick deactivation of the
system by sticking together of the catalyst pellets can be avoided.
The good activity and long-time behaviour of the NiNa-ZSM-5 catalysts could be ex-
plained:
by their high thermal stability
by their properties with respect to fluidized-bed conditions (e. g. low density)
by a favourable distribution of the nickel-particle size with respect to whisker formation (in
our case between 5 and 30 nm as could be proved by electron microscopy)
and possibly by the avoidance of formation of carbon forms other than whisker-like
Kinetics of the reaction follows a rate equation which contains the methane concentration
in a first order term and the hydrogen concentration in a second order one expressing the
reversible step. The activity of carbon does not appear in the rate equation and no inhibition
by hydrogen was observed. At the temperature which represents the region of highest activity
(about 1023 K ) a degree of conversion of nearly 0.9 can be realized (higher than the equili-
brium degree calculated from thermodynamic data).
REFERENCES
SUMMARY
Molybdenum sulfide and nickel-molybdenum sulfide catalysts
were prepared from Mo(CO), encaged in Y and stabilized HY zeolites.
These catalysts were characterized by XRD, IR, ESR spectroscopy and
NO sorption capacity. Mo(CO& based catalysts are highly reactive
in water-gas shift reaction and this is related to the high
dispersion of molybdenum sulfide. Ni and Mo containing zeolites
indicate the existence of synergetic effect. The synergy is
confirmed by the presence of a band at 2082 cm during adsorption
of CO. Catalysts prepared from dealuminated supports show low
activity, mainly due to the limited access of molybdenum carbonyl
into the zeolite cavities. ESR spectroscopy indicates the formation
of sulfur chain biradicals after interaction of HIS with
molybdenum containing supports.
INTRODUCTION
It is known that both high-temperature and low-temperature
water-gas shift catalysts, based on iron oxides and copper-zinc
oxides respectively, are highly sensitive towards sulfur
contamination of the feed. In order to overcome this problem a new
class of catalysts, similar to the hydrodesulfurization catalysts,
based on alumina-supported Co-Mo sulfides has been prepared and
recently introduced into the market.
Literature concerning the application of zeolites either as
catalysts or as the supports in water-gas shift (WGS) reaction is
scarce (ref.1-4). The Ru-X (ref.1) and Ru-Y (ref.2) zeolites have
been reported to be active in WGS reaction, but their activity and
especially stability were relatively low. Iwamoto et al. (ref.3)
studying transition metal ion-exchanged X and Y zeolites
established that only C U * ~and Ni” containing zeolites showed good
performance in WGS and this was related to the low electro-
negativity of the exchanged transition metal. Lee and co-workers
(ref.4) studying the kinetics of WGS reaction over Ni-Mo-Y-zeolite
catalysts in the sulfided state established high reactivity in this
reaction and excellent resistance against H,S and NH,.
378
EXPERIMENTAL
Mat er i a1s
NaY from KATALISTIKS (Si/A1=2.56) was applied as a starting
material for preparation of nickel and amonium exchanged zeolites.
The ammonium containing samples were obtained by a single or
multiple exchange with 0.25M aqueous solution of NH,C1 at 345 K.
Three series of stabilized Y-zeolites, denoted hereafter as USY-1,
USY-2 and USY-3, were prepared from NH4NaY forms, differing in the
degree of exchange, by hydrothermal treatment at 875 K for 4.5
hours under 100% steam. Nickel was introduced into the zeolites
before molybdenum by ion-exchange applying nickel nitrate solution,
both for NaY and USY series.
Molybdenum was loaded into the zeolites by saturation with
molybdenum hexacarbonyl vapours. Zeolitic supports after activation
at elevated temperatures in hydrogen were exposed to the Mo(CO),
vapours passing the support in a hydrogen stream for 10-15 hours at
room temperature. Samples completely saturated with Mo(CO), were
subsequently partially decarbonylated at 425 K for one hour in a
stream of hydrogen and next slowly exposed to the air at room
temperature with the use of leaking valve.
Each sample, before any experiment, was presulfided for two
hours at 675 K with a 10 vol.& mixture of hydrogen sulfide in
hydrogen, flowing with the rate of 2 dm3 h-'.
Chemicals a_nd Gases
Doubly sublimed Mo(CO), from Aldrich was used for saturations.
Hydrogen and helium were freed from impurities by passing through
379
TABLE 1
Characterization of Ni-, Mo- and Ni-Mo-Y zeolite catalysts
s-' ,
30Q 34
WAVENUMBER CM-1
A
b 1
3675 and 3590 cm-' appearing for
USY-3 can be attributed to the
hydroxyls connected with extra-
framework aluminum species (ref.
a 14). Nickel-containing ultrastabi-
BOO 170 lized samples showed additional
WAVENUMBER CM-' decrease of OH bands intensity,
similarily to the findings
presented in ref.14.
The characteristic OH bands formed upon nickel exchange with NaY
are shown in Fig.2. Here, after activation at 675 K the typical
acidic OH groups (3645 and 3554 cm-') are present. Activation at
475 K leads towards the appearance of new weak band at 3610cm-'.
This is usually ascribed to the characteristic dissociation of
water molecules over the zeolites containing divalent cations
(ref.13) with simultaneous formation of Me+(OH) species. Adsorption
of Mo(CO), at room temperature followed by thermal decomposition at
425 K yielded the subcarbonyl species with general formula cd
Mo(CO), (ref.8,15). Irrespective of the support used, after partial
decarbonylation, more or less complex infrared spectra in the
region of carbonyl groups vibrations were observed (example
presented in Fig.3.). Usually USY and HY supports give rise to the
more complex infrared spectra in the reg on of carbonyl vibrations
than for NaY or NaNiY samples. The decr ase in intensity of OH
bands for USY and NaNiY after partial decarbonylation at 425 K is
indicative of the oxidation of molybdenum by zeolite protons
(ref.5). Partially decarbonylated samples after intereaction with
H,S at room temperature show a significant reduction in the
383
carbonyl bands quantity (2031 sh, 1984, 1946 sh, 1845 cm-') and
absorbance value (see Fig.3.). Exposition of partially
decarbonylated samples towards H,S at 425 K resulted in a complete
disappearance of carbonyl groups and further decrease in the OH
bands intensity, suggesting the formation of sulfided molybdenum
species. Interaction with H,S at 675 K additionally lowered the
intensity of OH groups vibrations.
These observations show that after decarbonylation, interaction
with H,S at room temperature leads towards Mo(CO),-SH like species
(ref.8), whereas at higher temperatures,MoSx structures are formed
(1< x <2) (ref.16). Bands at 2530 and 2570 cm-' observed earlier in
similar systems for NaY support (ref.8) in our case were always
absent. Y-zeolites with Si/A1 ratio higher than 2.5 do not adsorb
H2S dissociatively (ref.17) and the absence of the band assigned to
H2S physisorption (2570 cm-') indicates a lack of this type of
interaction.
TABLE 2
Catalytic activity of the studied samples after 2 hours in WGSR
~ ~
NaY 1 28 1 32
2 16
3 21
NaN i Y 1 355 1 245 1 105
2 204 2 203
3 213 3 240
HNaY 1 74
HNaN i Y 1 83
USY-1 1 10 0.7 29 1 8
1 14
2 9
USY-2 0.7 28 0.7 34
USY-3 0.7 52 1 6
USY-1 -Ni 0.1 80 1 27
2 29
USY-2-N i 0.7 53
USY-3-N i 0.7 44 0.7 48 1 12
-- - ~ - -
384
CONCLUSIONS
(i) Mo- and Ni-Mo loaded Y-zeolites idicate high activity in
water-gas shift reaction in the presence of H,S.
( 1 1 ) Synergetic effect between Ni and Mo sulfided species for
water-gas shift reaction has been found.
( i i i ) Acidic OH groups of the support enhance catalytic activity in
water-gas shift reaction.
(iv) ESR measurements excluded the importance of M o ’ ~ ions in the
mechanism of WGS reaction over zeolitic sulfided catalysts.
REFERENCES
1 J.J. Verdonck, P.A. Jacobs and J.B. Uytterhoeven, J.Chem.Soc.
Chem.Comm., (1979) 181-182.
2 B.L. Gustafson and J.H. Lunsford, J.Catal., 74 (1982) 393-404.
3 M. Iwamoto, T. Hasuwa, H. Furukawa and S. Kaqawa, J.Cata1.
79 (1983) 291-297.
4 A.L. Lee, K.C. Wei, T.Y. Lee and J. Lee, in B.Imelik et al.
‘Eds.), Studies in Surface Science and Catalysis, -101.5,
Catalysis by Zeolites, Elsevier, Amsterdam 1980, pp.327-333.
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6 T. Komatsu and T. Yashima, J.Mol.Catal., 40 (1987) 83-92.
7 M. Laniecki, in H.G. Karge and J. Weitkamp (Eds.), Studies in
Surface Science and Catalysis, vo1.46, Zeolites as Catalysts,
Sorbeiits and Detergent Builders, Elsevier, Amsterdam, 1989,
259-269.
8 Y. Okamoto, A. Maezawa, H. Kane and T, Imanaka, J.Mol.Cata1..
52 (1989) 337-348.
9 M. Laniecki and W. Zmierczak, Zeolites, in press.
10 R. Moseler, B. Horvath, D. Lindenau, E.G. Horvath and H.L.
Krauss, Naturforsh., Anorq.Chem.,Org.Chem. 31B (1976) 892-898.
11 J. Arribas, A. Corma, V. Fornes and F. Melo, J.Catal., 108
(1387) 135-142.
12 R.D. Shannon, K.H. Gardner, R.H. Staley, G.Berqeret. P.
Gallezot and A . Auroux, J.Phys.Chem., 89 (1985) 4778-4781.
13 P. Jacobs and J.B. Uytterhoeven, J.Catal., 22 (1971) 193-203.
14 A . Ezzamarty, E. Catherine, D. Cornet, J.F. Hemidy, A . Janin,
J.C. Lavalley, J. Leglise and P. Meriaudeau, in P.A.Jacobs
and R.A.van Santen ( E d s . ) Studies in Surface Scie ce and
Catalysis, vo1.49B, Elsevier, Amsterdam 1989, pp. 025-1034.
15 Y. Okamoto, A. Maezawa, H. Kane and T. Imanaka Proc. 9th
International Congress on Catalysis, Calgary 1988,
V O l . 1 , pp.11-18.
16 M. Laniecki and W. Zmierczak, unpublished results
17 H.G. Karqe and J. Raskd, J.Coll.Interface Sc ., 64 (1978
522-532.
18 P. Hou, D. Mekker and H. Wise, J.Catal., 80 (1983 280-285.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 381
0 1991 Elsevier Science Publishers B.V., Amsterdam
1
Ji!?:EEJKA, Blanka WICHTERLOVd and Gloria LLabre RAURELL
The J. Heyrovsky Institute of Physical Chemistry and Electrochem-
istry, Czechoslovak Academy of Sciences, 182 23 Prague 8 ,
(Czechoslovakia)
'Chemical Research Center Cerro, La Habana (Cuba)
ABSTRACT
It has been found that H-forms of ZSM-5 zeolites differing in
the Si/A1 ratio exhibit straightforward relationship of activity
vs. para-selectivity in toluene alkylation to para-ethyltoluene.
Addition of Na, K and A1 cations or A1 oxidic species into the
zeolite cationic sites suppresses the zeolite void volume. This
results in an increase of para-ethyltoluene selectivity in the
initial alkylation step occurring in the channel intersections
and/or in a preferential transport of para-ethyltoluene from the
zeolite channels. Zeolite deactivation by coke is supported by the
presence of cations in the zeolite due to narrowing of the
channels or eventually due to their function as strong electron
acceptor sites. The coke formed in the zeolite does not enhance
the zeolite p<ira-selectivity and, moreover, for highly coked
zeolites a considerably lower para-selectivity is observed.
INTRODUCTION
Medium pore zeolites with pentasil type structures, such as
ZSM-5, -22, -23 and - 4 0 , are intensively studied as catalysts for
the alkylation, disproportionation and isomerization reactions of
alkylated aromatic hydrocarbons [refs.1-71. They exhibit high
selectivity for the formation of para-isomers that is often much
higher than that corresponding to thermodynamic equilibrium.
Toluene (T) alkylation with ethylene to para-ethyltoluene (p-ET)
seems to be a reaction of great industrial interest, because of
expected demand for para-methylstyrene [ref. 3 1 .
It has been observed that high selectivity for p-ET (far
exceeding the thermodynamic equilibrium value) can be attained at
low conversion level without any H-ZSM-5 zeolite modification
using the appropriate reaction conditions in contrast to H-Y
zeolites providing preferentially the ortho-isomer. This indicates
that the initial alkylation step into the para-position of toluene
for H-ZSM-5 zeolites is caused by steric hindrances already in the
zeolite channel intersections [ref. 4 1 . The further mechanism
388
EXPERIMENTAL
The parent ZSM-5 zeolites with Si/Al ratios ranging from 13.6
to 600 and oi: crystal size about 1 p m were supplied by the
Research Institute €or Oil and Hydrocarbon Gases, Czechoslovakia.
Acid forms of ZSM-5 zeolites were prepared by the ion exchange of
their N a forms with 0.5 M HN03 at ambient temperature. NaH-ZSM-5
and KH-2SI.I-5 'rlcrc prepared by ion exchange of H-ZSM-5 with 0 . 0 5 M
NaCl and 0.05 1.1 ICCl, respectively, at 350 K for 3 hours. Aluminium
was introduced into the H-ZSM-5 zeolites by ion exchange with 0.5M
Al(N03)3 (Alll-ZSM-5) or by impregnation with 1 M A1(N03)J
followed by calcination at 770 K in oxygen to provide
A1203H-ZSN-5.
The Si/Al ratio of the H-ZSM-5 zeolites used, the number of
strong acid bridqing hydroxyls and the sorption capacity for argon
f o r the 11- and modified ZSM-5 zeolites are given in the Table.
Fig. 1 depict.s the infrared (IR) spectra of the hydroxyl band
region for tt.e parent and modified zeolites. The IR spectra were
recorded on a FT-IR Nicolet MX-1E spectrometer. The zeolite void
volume was est-imated from the sorption capacity for argon measured
in a static apparatus at 13.33 kPa of argon at a temperature of 8 0
K on samples pretreated at 7 2 0 K in a vacuum of 10y4 kPa for 16
hours.
The alkylation of toluene with ethylene was carried out in a
vapour phase continuous down-flow microreactor at atmospheric
pressure and 623 K. Nitrogen as a carrier gas was saturated with
toluene at 3 3 3 K to 18.5 vol. %. The toluene to ethylene molar
ratio was 3.8. The reaction products were analyzed in on-line
arrangement by a Hewlett-Packard gas chromatograph with MS and FI
detectors using a supelcowax 10 capillary column. The toluene
conversion was normalized to 100 % of the theoretical conversion
corresponding t o a toluene to ethylene ratio 3.8. The details of
the catalytic measurements can be found in ref. 4 .
TABLE 1 Characteristics o f t h e z e o l i t e s used and t h e i r a c t i v i t i e s , p-ET s e l e c t i v i t i e s i n the
t o l u e n e a l k y l a t i o n w i t h e t h y l e n e a f t e r 15 m i n . of time-on-stream.
a
calculated value
390
100 I I 100
I AIB
100 100
75 75 $
v
3
c x
U
2vl 50
L
ti
6 25
t
1 1
15
I
55
I
95
I
135 175
T - 0 - S (mid
CONCLUSIONS
It can be summarized that the occurrence of the cations with
larger ionic radius than that of protons (Na, K, Al) in the
zeolite cationic sites as well as of some oxidic A1 phase
395
REFERENCES
1. L.R. Young, S . A . Butler and W.W. Kaeding, J. Catal. 7 6 ,
(1982) t l 8 .
2. W.W. Kaeding, C.-C. Chu, L.B. Young, B. Weinstein and S . A .
Butler, J. Catal. 6 7 , (1981) 153.
3. G. PaDarntto. E. Moretti, G . Leofanti and F. Gatti. J. Catal.
105, j l ? C 7 ) 227.
4. J. elks, R . Wichterlovg and S . Bedna/gova/, Appl. Catal.,
~~
submittcd.
5. W.W. Kaedincj, L.B. Young and C.-C. Chu, J. Catal. 89 (1984)
267.
6. I. Wang, C.-L. Ay, B.-J. Lee and M.-H. Chen, Appl. Catal. 5 4
(1989) 257.
7. P. Hatnnsaniy and S.K. Pokhriyal, Appl. Catal., 5 5 (1989) 265
8. N.Y. -
C h e n a n d W.E. Garwood, Catal. Rev. Sci. Eng. 28 (1986)
185.
9. J. Wei, J. Catal. 76 (1982) 4 3 3 .
10. L.M. Kustov, V . B . Kazansky, L. Kubelkovi, S. Beran and P.
Jir6, J. Phys. Chem. 91 (1987) 5247.
11. B. Wichterlovd, J. Novakovfi, L. Kubelkovi and P. Jirg, Proc.
5th 1nt.Zeol.Conf. Napoli (Ed. L . V . C . Rees) p. 373, 1980.
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 397
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
During the cracking process carbonaceous materials are
deposited on the outer or inner surface of the catalyst. These
deposits are in many cases the main cause of catalyst
deactivation. Magic angle spinning (MAS) NMR investigations and
catalytic n-hexane cracking were carried out o H-ZSM-5 zeolites
after a mild hydrothermal dealumination. By p 3 C CP MAS NMR it
could be shown that the enhanced catalytic activity does not
enhance the coke formation and that the chem’cal nature of these
deposits is essentially aromatic. From H’ MAS NMR tudies
qGrformed on shallow-bed activated sealed samples and 2$7Al and
Si MAS NMR on rehydrated samples it follows that for high coke
concentrations the catalyst deactivation is caused mainly by
blocking of Bronsted acid sites.
INTRODUCTION
The activity, selectivity and deactivation by coking have an
important influence on the industrial applicability of zeolites
(refs.1-7). In agreement with other authors (refs.9-11) in a
previous study (ref.12) using ‘HI 27Al and 29Si MAS NMR as well
as the catalytic cracking reaction of n-hexane we have found,
that a mild hydrothermal dealumination of zeolite H-ZSM-5 results
in an enhanced catalytic activity. Here we report ‘HI 13C, 27AL
and 29Si MAS NMR studies on such hydrothermal treated uncoked and
coked samples to elucidate where the carbonaceous products are
deposited. Whereas in some previous papers H-ZSM-5 was assumed to
produce coke preferentially on the external surface of the
crystallites (refs.13,14), recent studies give clear evidence of
coke formation in the interior pore system of the crystallites
(refs.15-19).
METHODS
Hvdrothermal treatment
The zeolite with a framework SifA1 ratio of 15 synthesized
without template was the same as used in ref.12. The hydrothermal
treatment of the binder free samples was carried out in a tube of
398
Catalvtic reaction
Catalytic activity was determined for the n-hexane cracking
reaction in an integral flow reactor. The reactor contained 0.259
zeolite in the form of binder free pellets with diameters of 0.3-
0.4mm. The catalyst was heated at a rate of 6K per min to 450OC
and then maintained at this temperature for lh in a hydrogen
flow. Since it is known, that the deactivation of H-ZSM-5
zeolites in the n-hexane cracking (refs.6,20,21) and methanol
conversion (ref.22) proceeds only slowly with hydrogen a s a
strem gas, we have used nitrogen (T=450°C,pN2=6kPa, pn-
hexane=92kPa). During the rection time of 15h a
gaschromatographic analysis of the reaction products was carried
out. If U denotes the relative molar conversion, the reaction
rate constant k is determined by the equation
k=-ln( 1-U) .
The conditions of the hydrothermal treatment as well as values
for the relative rate constant k/ko after coking are given in
Table 1. ko denotes the rate constant extrapolated to zero time.
Table 1
Conditions of hydrothermal treatment and values for relative rate
constant k/kO after n-hexane cracking for the samples under
study.
JWR measurements
13C, 27Al and 29Si MAS NMR measurements were generally carried
399
out on rehydrated samples. For the H ' MAS NMR measurements the
samples were pretreated under shallow-bed conditions in a glass
tube of 5.5mm inner diameter and with a bed-depth of lOmm for
zeolite material. The temperature was increased at a rate of 10K
per h. The samples were kept at the final activation temperature
of 4OOOC under a pressure below lOmPa for 24h, and than cooled
and sealed. Measurements were made on a homemade spectrometer HFS
270 and on a Bruker MSL 300 spectrometer. The homemade MAS
equipment for the rotation of the fused glass ampoules (ref.23)
was carefully cleaned to avoid spurious proton signals. As a
reference for the 27Al intensity measurements, a well-
characterized sample of H-ZSM-5 with a framework Si/Al ratio of
15 was used. The total concentration of OH groups in the
activated samples was determined by comparison of the initial
value of the free-induction decay of the sample with the
corresponding value for a standard (water). As a reference for
the 13C CP NMR intensity measurements a coked sample of H-ZSM-5
characterized by chemical analysis with respect to the carbon
content and the HjC ratio was used.
RESULTS
' MAS NMR
H
The H' MAS NMR spectra of the uncoked as well as of the coked
sample H-ZSM-510 are shown in Fig.1. Four different signals can
1a)'CHL
l H MAS NMR
Fig.1 H
' MAS NMR spectra of the sample H-ZSM-5/0 before (A) and
after (B) coking.
be seen. (i) The line (a) at 2ppm is due to non-acidic hydroxyl
groups at the outer surface of zeolite crystallites, at framework
400
Table 2
Concentration of protons and of framework aluminium atoms
2 9 ~ iMAS NMR
In Fig.2 29Si MAS NMR spectra are shown of the sample H-ZSM-
510 and of the hydrothermally treated sample H-ZSM-5/40 before
and after coking. A fitting procedure using the programm
lfLinesimlt yields three lines. It is well-known that the
unresolved signal of Si(OA1) groupings in zeolites ZSM-5 consists
of a peak at ca. -1llppm with a shoulder at ca. -115ppm. The line
at ca. -106ppm arises from Si(lA1) groupings (ref.25). The
framework SifAl ratio determined from the relation (ref.25)
401
4 4
Si/Al = 4* C Si(nAl)/nSi(nA1) C
n=O n=0
where Si(nA1) denotes the intensity of the NMR signal
attributable to Si(nA1) groupings is the same for both uncoked
and coked sample and agrees very well in the case of uncoked
samples with the result of the 27Al MAS NMR measurements.
29si MAS NVR
1
h
1 . I
-100
.
-120
I .
61m
I
Fig.2 29Si MAS NMR spectra of the sample H-ZSM-510 and the
1
Wpm
I
(B,D) coking.
MAS NMR
27~1
In Table 2 values are given for the number cAlfr. of framework
aluminium atoms per U.C. (columns ( 5 ) and ( 6 ) ) Because acid .
leaching was not performed, it is seen, that the coked samples
contain W M R invisible" aluminium.
LA
Fig.3 13C CP MAS NMR
spectra of the coked samples :
( A ) H-ZSM-510 before
heating at 400'C;
c
(B,C ,D ,) H-ZSM-510,
H-ZSM-5/10 and
H-ZSM-5/40, respectively
after heating the samples
up to 4OO0C;
(E) the same as Fig.3 (B)
but after total suppression
of the spinning sidebands
(TOSS) which are denoted by
asterisks in Figs.3(BIC,D). 300 200 100 0 6 PPm
DISCUSSION
Figs.1 and 3 as well as Table 2 (columns (1)-(6)) show
considerable changes in the 'HI 13C and 27Al spectra caused by
the coke formation in the channels of the H-ZSM-5 zeolites. The
decrease of the intensity of line (b) at 4.3ppm in the H
' MAS NMR
spectra and that of the line at -106ppm in the 29Si MAS NMR
spectra with increasing water vapor pressure for the uncoked
samples is caused by the dealumination of the zeolite (ref.12).
On the other hand, coking leaves the 29Si MAS NMR spectra
unchanged. That means, that in the n-hexane cracking process no
403
CONCLUSION
It has been shown in the present paper that besides the pulsed
field gradient technique (ref.16), the 27Al MAS NMR and the 29Si
MAS NMR (ref.17) the H
' MAS NMR spectroscopy with sealed samples
404
REFERENCES
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1986, Studies in Surface Science and Catalysis, Vol. 28,
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0 1991 Elsevier Science Publishers B.V., Amsterdam
.
J NOVAKOVA and L.KUBELKOVA
I
SUMMARY
HZSM-5 zeolite was completely deactivated during acetone
conversion at 35OoC as a result of the poisoning of bridging OH
groups by the coke deposit as well asobecause of pore
blocking.The coke residue was oxidized at 500 C to various degrees
and the restoration of hydroxyl groups and void volumes was
checked together with the changes in the remaining coke
deposit.The most pronounced changes in the adsorption properties
occurred when first coke layers were oxidized and the zeolite
pores were opened.The catalytic properties were renewed with the
reformation of bridging hydroxyls. During the oxidation, inter-
mediates of ketonic,carboxylate and carbonate character were
created,and decomposed yielding CO and COz.
INTRODUCTION
The coking of zeolites in catalytic reactionstwhich affects the
function of the active centers, depends on many factors, of which
the dimensions of the pores and cavities and their ordering are of
primary importance (refs.1-3) .The zeolite type has also been
found to influence the coke oxidation: in HY zeolitestthe coke was
oxidized at lower temperatures than that in HZSM-5 (refs.4,5) and
the CO,/CO ratio in the final oxidation products was higher
(ref.5). The access to coke deposits f o r the oxidizing agent and
the formation as well as the decomposition of oxygenated
intermediates probably play a decisive role in the coke
oxidation path.Consequently, the process of oxidation of coke in
a HZSM-5 zeolite was studied in more detail.
METHODS
NaZSM-5 zeolite (Si/A1=13.5) was supplied by the Research
Institute for Oil and Hydrocarbon Gases, Czechoslovakia, and was
transformed into the H-form by acid leaching (sample A).It was
406
RESULTS
Oxidation - coke c o m
The oxidation progress of the coked HZSM-5 (No l), yielding
partially oxidized samples N o s . 2-4, is depicted in Fig.1. The
partially oxidized sample No 2 exhibits the lowest oxidation level
and almost the same coke amount as the pyrolyzed sample 1' (TABLE
TABLE 1
Characteristics of coked, pyrolyzed and partially oxidized HZSM-5
in comparison with the parent uncoked zeolite
Sample Coke,wt% Oxidation level Void vol. Bridging OH ( % )
Ar ,mmol/g
A 0 - 5.2 100
1 10.7 0 0.1 16
1’ 9.2 0 0.2 19
2 9.7 0.07 2.8 34
3 515 0.49 3,8 65
4 1.5 0.86 5.3 93
value.The same behaviour can be seen in the values of the LTP (low
temperature peak) for ammonia desorption (Fig.4a).The LTP of
benzene also exhibits a lower value for sample No 2 (Fig.4b).
Isotope exchange
The kinetics of the isotope exchange of deuterium between
perdeuterated benzene and the hydrogens of OH groups and coke
residues is shown in Fig.5.It can be seen that a plot of the In of
the concentration vs. time obeys a first order law for samples A
and 2-4, while a strong deviation is visible for the completely
coked zeolite (1) and its pyrolyzed form (lt).Fig. 5 also shows
that the exchange rate is slower for the hydrogen atoms of coke
than for the hydroxyl groups. The number of H atoms participating
in the exchange is given in TABLE 2. The calculation was based on
the exchange equilibrium values obtained after 15 h of
reaction and the known amount of benzene employed in the exchange:
N = M * (co-coo)/coo (1)
where N is the number of H atoms participating in the exchange
with M deuterium atoms of benzeneland co and coo are the
concentrations in times to and too,respectively.
TABLE 2
Catalytic activity
The restoration of the active centers for acetone conversion
(strong Bronsted acid sitestbridging hydroxyls (refs.7,8))
exhibits different behaviour than the restoration of void
volumes. The acid centers are renewed in closer proportion to the
decrease in the coke amount (increased oxidation level) which can
be seen in TABLE 1 and Fig.4a (HTP -high temperature peak- of
ammonia desorption). The HTP of benzene seems not to reflect only
the number of strong acid centers.
The reformation of the catalytic activity of the zeolites
studied can be seen in Fig. 6. In this Fig. , the TPC curves are
shown for the parent HZSM-5 (A) and samples 1,1t,2,3 and 4. In
agreement with the above described adsorption properties, the
amount of physically adsorbed acetone (i.e. not converted,
released with maximum rate at 75OC ) is low for samples 1 and l t ,
411
but high and almost the same for the remaining samples. However,
this is not true for the catalytic transformation of preadsorbed
acetone. It follows from Fig. 6 that the restoration of the
catalytic activity corresponds to the number of freed OH groups.
4
0 200
Fig.5. (left) Isotope exchange of C6D6 with the hydrogen of the
OH groups and of coke at 30OoC. F= (co- Ct )/(co - Coo); COfCt,
and coo are concentrations of D atoms at times toft and
too,respectively.
Fig.6.(right) TPC of preadsorbed acetone.- acetone,--isobutene,
.
. .C O ,~Iaromatics.
DISCUSSION
Effect of partial oxidation on the coke composition and zeolite
void volumes
Both the pyrolysis of the completely coked HZSM-5 and partial
oxidation result in some similar changes in the coke:in the
removal of the alkyl substituents on the aromatic rings and the
remainders of the acetone conversion intermediate as well as in
the decrease of the light aromatic coke components ( especially
after the pyrolysis). It can be concluded that the oxidation of
these three coke components proceeds more readily than the
412
REFERENCES
1 D.E. Walsh and L.D. Rollmann, Radiotracer experiments on carbon
formation in zeolites.11, J.Catal.,56 (1979) 195-197 and
references therein.
P-Magnoux, P.Cartraud, S.Mignard and M.Guisnet, Coking,aging
and regeneration of zeolites, J.Catal.,l06 (1987) 242-250.
M.Guis.net and P.Magnoux, Coking and deactivation of
zeolites,Appl. Cata1.,54 (1989) 1-27,and references therein.
P.Magnoux and M.Guisnet, Coking,ageing and regeneration of zeo-
1ites.VI. Comparison of the rates of coke oxidation on
HY,H-Mordenite and HZSM-SIAppl.Catal.,38 (1988) 341-352.
5 J.Novakova and Z.Dolejsek,A comment on the oxidation of coke
deposited on zeolites,Zeolites,lO (1990) 189-192.
6 J.Novakova,L.Kubelkova,V.Bosacek and K.Mach, Zeolites,in press.
7 J.Novakova,L.Kubelkova,P.Jiru,S.Beran and K. Nedomova, A study
of the interaction of some ketones with HZSM-5 zeolite,
Proc.Int.Symposium on Zeolite Catalysis,Siofok,Hungary,May 13-
-16,1985,Acta Physica et Chemica SzegediensisIl985,pp.56l-578.
8 L.Kubelkova,J.Cejka,J.Novakova,V.Bosacek,I.Jirka and P.Jiru,
Acetone conversion and deactivation of zeolites, in:
P.A.Jacobs and R.A.van Santen (Eds), Zeolites: Facts, Figures,
Future,Elsevier, Amsterdam,1989,pp.l203-1212.
9 H.G.Karge,E.P.Boldingh,J.-P.Lange and A.Gutsze,Studies on coke
formation on dealuminated mordenites by in-situ IR and EPR me-
asurements,Proc. Int. Symposium on Zeolite Catalysis,Siofok,
Hungary, May 13-16,1985,Acta Physica et Chemica Szegediensis,
1985,pp.639-648.
414
l C e n t r a 1 I n s t i t u t e o f P h y s i c a l Chemistry o f t h e Academy
o f Sciences
zLeuna-Werke AG, 4220 Leuna 3
SUMMARY
Samples o t P-modified LSM-5 t y p e z e o l i t e p r e v i o u s l y d e a l u m i n a t e d
by steaming a t d i f f e r e n t temperatures were used as c a t a l y t i c a l l y
a c t i v e components i n t h e c o n v e r s i o n o f methanol t o l o w e r o l e f i n s
a t 5bO"C. R e s u l t s show t h a t d e a l u m i n a t i o n a t 400°C f o l l o w e d by
t r e a t m e n t w i t h 2 N n i t r i c a c i d a l l o w s h i g h e s t degrees o f p a r t i a l
e x t r a c t i o n o f non-framework aluminium and o f f e r s b e s t r e s u l t s w i t h
r e s p e c t t o s e l e c t i v i t y o f C z / C 4 - o l e f i n s and c a t a l y s t s t a b i l i t y .
INTRODUCTION
LSM-5 t y p e z e o l i t e s a r e a p p r o p r i a t e c a t a l y s t s f o r t h e methanol-
to-olefin conversion (1-5). Cz/C4-olefins reach s a t i s t y i n g
s e l e c t i v i t i e s , P r o v i d e d t h a t t h e ~ l / A l F r - a r n e ~ ~( ~S -i /kA l F ) r a t i o i s
sufficiently h i g h . S e l e c t i v i t y o f o l e f i n s can be i n c r e a s e d
a d d i t i o n a l l y by t r e a t i n g t h e samples w i t h p h o s p h o r i c a c i d ( 6 - 1 0 ) .
Even w i t h those P-modified z e o l i t e s , h i g h v a l u e s o f t h e S i / A l F
r a t i o e x e r t a p o s i t i v e e f f e c t on t h e f o r m a t i o n o f t h e d e s i r e d
olef ins.
Besides by a p p r o p r i a t e a d a p t a t i o n o f t h e c o n d i t i o n s o f s y n t h e s i s
i t s e l f , aluminium d e f i c i e n t z e o l i t e s can be o b t a i n e d by h i g h tem-
p e r a t u r e c a l c i n a t i o n o r steaming o f samples which o r i g i n a l l y con-
t a i n a h i g h e r f r a c t i o n o f aluminium (11). The degree o f dealuniinu-
t i o n s t r o n g l y depends on t h e e x p e r i m e n t a l c o n d i t i o n s under which
t h e steaming o t t h e sample Proceeds. BY v a r i a t i o n o f t e m p e r a t u r e
416
EXPERIMENTAL
PrePara.tiPc! . . o ~ f s n m f l ~ .
P e n t a s i l t y p e ZSM-5 z e o l i t e (HS-30, Si/A1=19, Chemie AG B i t t e r -
f e l d ) i s c o n v e r t e d i n t o t h e H+-form by a f o u r t i m e s r e p e a t e d
t r e a t m e n t w i t h a 0 . 2 N s o l u t i o n o f HNOs i n a s i m p l e b a t c h p r o -
cedure. F o r d e a l u m j n a t i o n , t h r e e s e p a r a t e samples o f t h e Hi-form
a r e exposed t o a stream o f a i r and steam (pweter=90 kPa) a t 400,
470 and 700OC. To a c h i e v e a p p r o x i m a t e l y i d e n t i c S i / A l F r a t i o s ,
t i m e o f steaming was 70. 6 and 0.25 hours, r e s p . Framework a l u m i -
nium o f each sample was d e t e r m i n e d u s i n g t h e ammonium exchange
methode (11). Subsequently P a r t o f each o f t h e samples was t r e a t e d
w i t h 2 N HN03 a t 103°C f o r p a r t i a l e x t r a c t i o n o f non-framework
aluminium formed d u r i n g d e a l u m i n a t i o n . E x t r a c t e d aluminium was
determined a n a l y t i c a l l y i n t h e s o l u t i o n o f t h e e x t r a c t i n g a g e n t .
C a t a l y s t p a r t i c l e s were p r e p a r e d by m i x i n g t h e HS-30 samples w i t h
A e r o s i l - 2 0 0 and water and subsequent e x t r u d i n g , t h e ready made
e x t r u d a t e s (6 = 1 t o 2 mm) c o n t a i n i n g 65% by w e i g h t o f z e o l i t e . P-
m o d i f i c a t i o n was c a r r i e d o u t by i m p r e g n a t i o n w i t h aqueous phospho-
r i c a c i d . The c o n t e n t o f phosphorus f o r c a t a l y s t s based upon
417
(;o.tnlY 51s
Catalytic experiments were carried out in a tubular fixed bed
reactor ($ = 12 mm) using a mixture of methanol/Nz (molecular
ratio= 1 : l ) as reaction feed (conditions o f reaction see table 1).
Products were analyzed by an on-line operated gaschromatographic
device. Calculation o f the concentration from analytical data is
based on individual calibration of the components.
t einpera t u r e : 560°C
concentration of methanol: 50 Vol-%
catalyst volume: 10 ml
catalyst mass: 5.0
feed rate (mixture): 3.33 ml/s (STP)
c h.at-a
GHSV(mixture) : 1200 ml/mlcataivst*h
LHSV(methano1): 1 ml/mlcata~ystffh
.. .- . . . . ~~~ . . . . .. .. . -. . . . . .
Photoelectron spectrosc.oPr
XPS investigations were carried out with an AEI ES200B electron
spectrometer, using MgKd radiation. Resulting signal intensities
required a spectra accumulation based on the PDP8e/DS800 data
system. Ine analyzer system ot the spectrometer was calibrated
according to Anthony and Seah ( 1 3 ) . Evaluation of XPS intensity
ratios to derive atomic ratios on the surface was based on the
model of homogeneous distribution (14).
r ecorded by a c o n v e n t i o n a l d e v i c e .
Temperature Programmed o x i d a t i o n
Carbonaceous d e p o s i t s formed d u r i n g r e a c t i o n on t h e c a t a l y s t
were det ermin e d by te mp e ra tu re Programmed o x i d a t i o n . Coke was
burned oft i n a stream o t d r y a i r i n t h e t e m p e r a t u r e range between
200 and 700 OC, t h e heat r a t e b e i n g 5 " C h i n . T h i s p r o c e s s was
monit ored c o n t i n e o u s l y by r e c o r d i n g c a r b o n monoxide and d i o x i d e .
The o x i d e s were s e p a ra te d by a Cekatron 5 column and d e t e r m i n e d
g aschromot ogr a p h i c a l l y a f t e r c o n v e r s i o n t o methane. Carbon ( m c )
was c a l c u l a t e d from t h e t o t a l amounts o f t h e o x i d e s .
RESULTS
Experiment al r e s u l t s o f methanol c o n v e r s i o n w i t h t h e s i x c a t a -
lysts based on HS-30 samples o f d i f f e r e n t P r e p a r a t i o n a r e r e p r e -
sented i n t a b l e s 2 and 3 . Values o f p r o d u c t s e l e c t i v i t y a r e r e l a -
t e d to t h e p o r t i o n s o f carbon o f fe d methanol w h i c h a r e c o n t a i n e d
i n t h e g i v e n component o f t h e p r o d u c t :
TABLE 2: E f f e c t o f steam d e a l u m i n a t i o n on p r o d u c t s e l e c t i v i t i e s
and c a t a l y s t s t a b i l i t y
Non-extracted HS-30 z e o l i t e
Content o f phosphorus 1 . 5 w t - %
TABLE 3: E f f e c t o f steam d e a l u m i n a t i o n on p r o d u c t s e l e c t i v i t i e s
and c a t a l y s t s t a b i l i t y
E x t r a c t e d HS-30 z e o l i t e , c o n t e n t o f phosphorus 1.1 w t - %
p roduct s e l e c t i v i t i e s X
e t hene 17,O 18,9 19,5
Propene 37,6 30,6 27,9
b u t enes 25,l 18,5 16,9
- - - - - - - _ - - - - - - - - - - - - - - - - _ - - - - - - - _
CZ/& olefins 79,7 68,O 64,4
ti me o f d e a c t i v a t i o n ( h ) 96 68 33
- . ... -
butenes. S e l e c t i v i t y o f ethene i s n o t n e g a t i v e l y i n f l u e n c e d as
t i m e o f d e a l u m i n a t i o n i s decreased: I n c o n t r a s t t o Propene and t h e
butenes i t s v a l u e s l i g h t l y i n c r e a s e s w i t h d e c r e a s i n g t i m e o f stea-
ming. I t i s w o r t h m e n ti o n i n g t h a t e x t r a c t i o n o f non-framework a l u -
minium f avou rs t h e f o r m a t i o n o f methane, b u t s l i g h t l y suppresses
t h e accumulati o n o f C s - a l i p h a t e s .
F or p r a c t i c a l purposes o f t h e methanol c o n v e r s i o n , a c a t a l y s t ba-
sed on an e x t r a c t e d , P-modified ZSM-5 z e o l i t e p r e v i o u s l y dealumi-
nat ed by steaming a t temperatures i n t h e r e g i o n o f 4000C s h o u l d be
P r e f e r e d . S e l e c t i v i t y o f l o w e r o l e f i n s and c a t a l y s t s t a b i l i t y
a chieve a t t r a c t i v e v a l u e s .
D e t e r m i n a t i o n o f coke on spend c a t a l y s t s ( Ta b l e 4) r e v e a l s t h a t
t h e r a t e o f coke d e p o s i t i o n i s h i g h e r w i t h t h e n o n - e x t r a c t e d sam-
p l e s . These c a t a l y s t s , a l t h o u g h performed o v e r a d e f i n i t e l y
s h o r t e r t i m e th a n t h e i r e x t r a c t e d c o u n t e r p a r t s , show p r a c t i c a l l y
i d e n t i c amounts o f coke. The s u p p re s s i o n o f t h e d e p o s i t i o n o f coke
i s o b v i o u s l y due t o t h e removal o f non-framework aluminium,
because t h e e f f e c t i s found w i t h b o t h P-modified and P - f r e e
catalysts.
ti m e o f d e c t i v a t i o n amount o f coke d e p o s i t e d
Catalyst I hours ) (mgcoke/gzeoli te)
31,5
35,8
8 119,4
10 126,s
12 114,3
26 110,6
The e v a l u a t i o n o f XPS d a t a (T a b l e 5) r e v e a l s t h a t w i t h t h e p a r e n t
HS-30 z e o l i t e t h e S i / A l r a t i o on t h e s u r f a c e i s h i g h e r t h a n t h e
average S i / A l v a l u e d e r i v e d from NHe+-exchange d a t a . D i s t r i b u t i o n
o f aluminium over t h e c r y s t a l i s s l i g h t l y inhomogeneous. W i t h t h e
dealuminated samples, d i f f e r e n c e s between t h e s u r f a c e and t h e
422
TABLE 5 : XPS i n v e s t i g a t i o n , r e l a t i v e X P S i n t e n s i t i e s
( d e v i a t i o n f 10%). Hs-30
average S i / A 1 r a t i o a r e c o n s i d e r a b l e . S u r f a c e v a l u e s a r e c l e a r l y
s h i f t e d i n fa v o u r o f t h e a c c u m u l a ti o n o f a l u m i n i u m . B o t h samples
have n e a r l y i d e n t i c S i / A l F r a t i o s and t h e r e f o r e do n o t d i f f e r i n
t h e i r t o t a l amounts o f non-framework a l u m i n i u m . The s t r o n g d e v i a -
t i o n s o f t h e r e l a t i v e X P S i n t e n s i t i e s between t h e two d e a l u m i n a t e d
samples show t h a t d i s t r i b u t i o n s o f non-framework a l u m i n i u m a r e
d i f f e r e n t . I t can be assumed t h a t d e p o s i t i o n o f a l u m i n i u m on non-
microporous s u r f a c e areas, i . e . i n t h e system o f mesopores o r on
t h e e x t e r n a l s u r f a c e area, i s fa v o u re d by l o n g t i m e steaming.
The t o t a l number
of acid sites i s
i n c r e a s e d by ex-
traction. This >
can be seen from
the results o f
I
:,
(
$
temperat ure p r o - 3
srammed desorp- :.
t i o n o f ammonia i
o f the P-f r e e
zeolite (Fig.1). 7"
lhe amount o f
ammonia adsorbed 2& jw h c o
-
,oo T / '2 200 100 .:OO 5W
1
D93 dealuminated HS-30 ( S i / A 1 ~ = 9 3 ) Dealurnination
D93E d e a l u mi n a te d e x t r a c t e d Hs-30 a t 4000 C
(degree o f e x t r a c t i o n
- - - - - - - - - - - - - - - - - - - ._ f o r 70 h
I
= 22%)
D e e dealuminated HS-30 ( S i / A 1 ~ = 8 6 ) Dealumination
D e 6 E dealuminated e x t r a c t e d HS-30 a t 7000C
(degree o f e x t r a c t i o n = 6%) for 0 2 5 h
423
DiSCbSSlUN
.The e x p u l s i o n o t t e t r a h e d r a l aluminium from s u b s t i t u t i o n a l P o s i -
t i o n s i n t h e framework o f s i l i c a g i v e s r i s e t o t h e f o r m a t i o n o f
non-framework aluminium o f v a r i o u s c h e m i c a l n a t u r e ( 1 2 ) . Aluminiiiin
species w i t h t e t r a h e d r a l l y and o c t a h e d r a l l y c o o r d i n a t e d c e n t r a l
i o n s ( 1 s ) o f d i f f e r e n t degrees o i a g g r e g a t i o n a r e d e p o s i t e d i n t h e
z e o l i t e channels and channel i n t e r s e c t i o n s . M i g r a t i o n t o t n e
e x t e r n a l s u r f a c e i s p o s s i b l e . I t can be assumed t h a t P a r t i a l
b l o c k i n g o f pores by a e p o s i t s can cause a h i n d r a n c e o f t h e d i f f u -
s i o n o f t h e p r i m a r y p r o d u c t s o u t o f t h e p o r e system t h u s i n c r e a -
s i n g the p r o b a b i l i t y o f f u r t h e r undesired reactions o f the
o l e f i n s . Besides, i t cannot be excluded t h a t non-framework a l u m i -
nium i t s e l f o r - as i n o u r case - aluminium phosphates formed by
i n t e r a c t i o n w i t h t h e p h o s p h o ri c a c i d a r e c a t a l y t i c a l l y a c t i v e ,
P o s s i b l y e n a b l i n g h y d r i d e t r a n s f e r w i t h t h e o l e f i n s o r any o t h e r
b y - r e a c t i o n s o f t h e feed component.
C a t a l y t i c r e s u l t s show t h a t w i t h n o n - e x t r a c t e d samples t h e v a r i a -
t i o n o f t h e c o n d i t i o n s o f d e a l u m i n a t i o n has no s i g n i f i c a n t e f f e c t
on t h e d i s t r i b u t i o n o f p r o d u c t s . D i f f e r e n c e s w i t h r e s p e c t t o Pore
t r a n s p o r t phenomena and t o o t h e r i n f l u e n c e s o f t h e non-framework
alumina on t h e f o r m a t i o n o f a n a l y t i c a l l y determined p r o d u c t s a r e
n e g l i g i b l e . i t i s , however, e v i d e n t t h a t t h e f o r m a t i o n o f h i g h l y
condensed compounds (carbonaceous d e p o s i t s . coke) i s a f f e c t e d by
t h e n a t u r e o f non-framework aluminium. Dealuminated z e o l i t e s
o b t a i n e d by s h o r t ti me steaming undergo t h e most r a p i d d e a c t i v a -
t i o n , as i s shown by t h e v a l u e s o f t i m e on stream and c o n f i r m e d by
t h e d e t e r m i n a t i o n o f d e p o s i t e d coke.
The dependence o f t h e degree o f e x t r a c t i o n o f non-framework a l u m i -
nium on t h e c o n d i t i o n s o f d e a l u m i n a t i o n c l e a r l y shows t h a t l o n g
ti me steaming o t t h e z e o l i t e d u r i n g d e a l u m i n a t i o n f a v o u r s deposi-
t i o n o t aluminium i n Places o f good a c c e s s i b i l i t y t o l i q u i d
a g ent s. With growing t i m e o f d e a l u m i n a t i o n t h e f r a c t i o n o f non-
framework aluminium whicn can m i g r a t e i n t o t h e r e g i o n o f pore-
mouths o r t o t h e e x t e r n a l s u r f a c e a re a i s r a i s e d . T h i s assumption
Is supported by t h e r e s u l t s o f p h o t o e l e c t r o n spectroscopy ( X P S ) .
l h e h i g h e s t Al/Si r a t i o on t h e e x t e r n a l s u r f a c e i s found w i t h t h e
sample steamed Tor 72 h o u r s .
424
REFERENCES
1 C.D.Chang, C a t a l . R e v . - S c i . E n g . 2 5 , 1. l ( 1 9 8 3 )
2 C.D.Chang, C a t a l . R e v . - S c i . E n g . 2 6 , 3 / 4 . 223(1984)
3 V.Ducarme. J . C . V k d r i n e . A ~ ~ l . C a t a l . 1 7175-84(1985)
.
4 N.Y.Chan, W.E.Gorwood, C a t a l . K e v . - S c i . E n g . 2 8 , 185-264(1986)
S P.Jarlagadda, C.F.R.Lund, E . R u c k e n s t e i n , A p p l . C a t . 5 4 , 135(1989)
6 L.B.Young, S . A . B u t t e r . W.W.Kaeding, J.Cata.L.76, 418-432(1982)
i J . C.Vedrine, A . Auroux, P . D e J a i t r e , V . I)ucarire, n . H O S e r , 5 . Lliou
J . C a t a 1 . 7 3 , 147-160(1982)
8 L.W . Z a t o r s k y , P . r . Wierzchowski. A . A . Cichowtas. 61111. P o l i s h
Acad.Sciences, Chemistry, 32, 217-222(1984)
9 .J . A . I - e r c h e r . G . R~JmolmflVr. H .N o l l e r - . Acto Pbvs. Cheni. 5 1 , 71(1(485)
10 S h i g e r u I k a i , Manabu Okomoto. A u p l . C a t . 4 9 . '143(1989)
11 G.ohlaann, H.-G.Jerschkewitz, G.Lischke, b . P o r l i t z , K . t c k e l t ,
M . H i c h t e r , L . t.Cheinie 28, 5, 161-168 (1988)
1 2 J .Scherzer i n C a t a l y t i c M a t e r i a l s , ACS SYinposiuni S e r i e s 248,
157, Washington D . C . 1984
1 3 M.T.Anthony, M.P.Seah. S u r f . I n t e r f a c e A n a l . 6 . 95(1984)
14 M.P.Seah, i n P r a c t i c a l S u r f a c e A n a l y s i s ( t d s . D . B r i g g s . M . P .
Seoh). W i l e y . 1983. ChaD.5
1 5 A.Samoson, E.Lipmaa, G . t n g e l h a r d t , U.Lohse, H . - G . J e r s c h k e w i t z
Chem.PhYs. L e t t e r s 134, b, 589(1987)
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 425
0 1991 Elsevier Science Publishers B.V., Amsterdam
ABSTRACT
The influence of different hydrothermal treatment conditions of
HZSM-5 on the n-hexan cracking activity wa5 studied. The Bronsted
and Lewis acid sites were characterized by diffuse reflectance IR
spectroscopy using various probe molecules. The spectroscopic and
catalytic results were discussed with t h e emphasis to t h e role of
Lewis sites in the activity enhancement after steaming and in the
mechanism o f t h e paraffin cracking.
INTHODUCTION
The influence of hydrothermal treatment on the properties of
zeolites is of particular interest from the point of view of
preparation of cracking catalysts with high activity, selectivity
and stability. Recently, an effect of a considerable enhancement
of t h e cracking activity for HZSM-5 zeolites pretreated under mild
steaming conditions was reported (refs. 1-3). It was explained
(ref. 1 ) b y a strengthening of acidic properties of a part of
bridged OH groups. However, hydroxyl groups exhibiting acidic
properties stronger than OH groups of t h e initial zeolite have not
been detected (refs. 1-3). In the present work the nature and
properties of Bronsted and Lewis acidic sites in HZSM-5 zeolites
deal urn1 nated under mi 1 d o r severe hydrothermal condi ti o n s are
studied by the highly sensitive method of diffuse reflectance IR
spectroscopy. Different probe molecules ( H2 , CH4, CH3CN) a r e used
t o characterize the Lewis acidic sites.
EXPERIMENTAL
The H Z S I I - 5 zeolite (Si/A1=18) was treated with water vapour
under mild (T = 810 K , pHz0 = 1.3*104 Pa,t = 10-150 min) or severe
426
5
conditions (T = 770 K, pH = 10 Pa, t = 1.5 - 24 h). Before
2
spectroscopic or catalytic measurements the samples were
pretreated at 690 - 770 K for 4 h in vacuum or in He stream.
Diffuse reflectance IR spectra were measured using Perkin Elmer
580 B and Beckman Acta M V I I spectrophotometers according to the
procedure described by Kazansky et al. (ref. 4). Transmission
measurements were carried out on an IR spectrometer SPECORD M80
(Carl-Zeiss-Jena GmbH). For identification of Lewis acid sites t h e
low temperature adsorption of molecular hydrogen (ref. 4) a s well
a s the adsorption o f methane (re+. 5 ) and acetonitrile (ref. 6 ) at
300 K were used. The catalytic data were obtained using a flow
reactor with on-line GC-analysis of t h e products. Mixtures of
n-hexane and I-hexene were used as feeds with olefin
concentrations varying from to 10 vol %. The reaction
temperature ranged from 670 t o 770 K.
kt'ko I
*i
361 0
3665 I
3610
I
3700 3600
-3/cm-1
3500 3700
-3600 3500
3 / c m -1
2 308
I
\
-
2400
-
2300 2200
31cm-1
Fig. 3. Transmission IR spectra of
CH3CN adsorbed on t h e fresh HZSM-5
zeolite (1) and on zeolites steamed
under mild conditions: (2) t = 10 min
and (3) t = 150 min.
3010
3080 I
&110
I
hOB0 4035
- d
Slcrn-1 ---v/cm
-, -1
'10 o f C6H12
CONCLUSION
Depending on t h e conditions of hydrothermal treatment different
acid sites appear in HZSM-5 zeolites due to the formation of
non-framework aluminium. Most of these species are hydroxylated
fragments with acidic properties weaker than those of bridged
OH-groups. Only a small part of non-framework A1 exhibits the
properties of Lewis acid sites.
In our opinion Lewis acidic sites connected with non-framework
aluminium which are capable to polarize C-H-bond in alkane
molecules a r e t h e active s i t e s responsible for t h e acceleration of
t h e initial stage of cracking via alkane dehydrogenation or
demethanation. The optimum in t h e cracking activity observed for
HZSM-5 zeolites dealuminated under mild steaming conditions could
b e interpreted in terms of t w o competitive tendencies:
i ) acceleration of t h e rate-determining step of initiation due
t o an increasing concentration of non-framework Lewis acid sites
and
i i ) inhibition o f cracking via the disappearance of Bronsted
acid sites during steaming pretreatment which a r e also involved
into t h e reaction. In our opinion these s i t e s take part in the
cracking process a s centres responsible for t h e transformation of
formed olefinr via t h e classical carbenium ion mechanism.
T h u s t h e former trend results in an increase of activity at t h e
very beginning of dealumination whereas t h e latter trend which is
well-pronounced at t h e middle o r final stages of steaming leads t o
a loss of activity. Therefore, t h e highest catalytic activity and
t h e best cracking performance of HZSM-5 zeolites could be reached
433
REFERENCES
1 R.M. Lago, W. 0.Haag, R. J. Mi kovsky, D. H. Olson, S. D. He1 Iring,
K.D.Schmitt, G.T.Kerr, Proc. 7th Int. Conf. on Zeolites,
1986, Tokyo , p.677.
E. Brunner, H.Ernst, D.Freude, T.Froh1 ich, M. Hunger, H. Pf eif er,
Stud. Surf. Sci. Catal., 1989 , v.49 , part CI ,p.623.
V.L. Zholobenko, L. M. Kustov, V. B. Kazansky, E. Loef f ler, U.
Lohse, Ch. Peuker, G. Oehlmann, Zeolites, 10 (1990) 304-306.
V.B.Kazansky, V.Yu.Borovkov, L.M.Kustov, Proc. 8th Int. Congr.
on Catalysis , West Berlin , 1984 , v.3 , p.3.
V.L.Zholobenko, L.M.Kustov, V.B.Kazansky, Dokl. CIN SSSR, 300
( 1988), 384-388.
E. A.Paukshtis, R. J. Sol tanov, E. N. Yurchenko, React. Ki net.
Catal. Lett., 23 (1983) 339-342.
E.Loeffler, U.Lohse, Ch.Peuker, G.Oehlmann, L.M.Kustov,
V.L.Zholobenko, V.B.Kazansky, Zeolites, 10 (1990) 266 - 271
H-Kriegsmann, A-Reklat, E.Loffler, Th.Steiger, Z. phys. Chemie,
Leipzig, 271 (1990) 61-67
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 435
0 1991 Elsevier Science PublishersB.V., Amsterdam
K.-P. SCHRBDER
Central Institute of Physical Chemistry, Academy of Sciences of the GDR,
DDR-1199 Berlin-Adlersliof (GDR)
ABSTRACT
The method of molecular mechanics is used to model pxylene sorption in
ZSM-5/silicalite-l on the basis of empirical atom-atom potentials. The
experimental atomic coordinates of both monoclinic and highly gxylene-loaded
orthorhombic ZSM-5 were taken into account. Considerable differences with
respect to the sorption properties were found. It is concluded that the
framework structure is locally changing already at very small amounts of sorbed
yxylene. There exist two types of pxylene molecules at maximal loading. The
XYLl molecule is highly mobile with respect to diffusion along the straight
channel, whereas the mobility of the XYLZ molecule in the sinusoidal channel is
significantly more restricted.
INTRODUCTION
The three-dimensional pore system of the silicon-rich zeolite ZSM-5 consists
of straight channels parallel to [ O l O l interconnected by sinusoidal channels in
[loo] direction, both built of ten-membered rings. The pore diameters are of a
size similar to the kinetic diameters of aromatic molecules such as benzene and
xylene. Thus the mobility of aromatic molecules in ZSM-5 is restricted (refs.
1-41 and a complicated dependence of the differential heats of sorption on pore
filling is observed (refs. 5-8).
One of the most interesting features of ISM-5 is its reversible
transformation between monoclinic and orthorhombic crystal structures.
As-synthesized ZSM-5 including template is orthorhombic with Pnma space group
(ref. 9). H-ZSM-5 and its aluminium-free form silicalite-1 are monoclinic. A
transformation to orthorhombic symmetry occurs on increasing the temperature up
to 320 - 360 K (refs. 10-13) or on loading with various molecules (refs.
9,14,15) including aromatics.
This change of crystal structure has been neglected in previous computer
modelling studies (refs. 8,16-23) of sorption and diffusion of aromatic
molecules in ZSM-5/silicalite-l, which assumed rigid frameworks.
A theoretical study of the packing arrangement of pxylene in a ZSM-5 type
framework has been performed by Reischman et al. (ref. 2 0 ) . The atomic
coordinates of Olson et al. (ref. 2 4 ) with Pnma space group were used. On the
basis of an empirical atom-atom potential due to Williams and Starr (ref. 25)
the interaction energies of a pxylene molecule with the framework in the
436
CALCIJLATIONS
Stable sorbate structures correspond to minima of the potential energy
surface for the interaction between the zeolite framework and sorbed molecules.
The interaction energy is represented in this study by a pairwise additive
atos-atom potential function. The energy for the sorbent-sorbate interaction is
calculated using a Lennard-Jones type potential,
AE = r (-A
at?
r -.6. + Bap r -12
I J
, ,) ,
I J
i j
and that for the interaction between pxylene molecules using a Buckingham type
potential,
437
The index i runs over all atoms in the framework cut-out, indices j and k over
all atoms in different pxylene molecules, r . is the interatomic distance. The
11
empirical parameters AaS, BaB and C characterizing the interaction between
aB
atoms of the type a and p are taken from Kiselev et al. (ref. 29) for the
Lennard-Jones type potential and from Williams and Starr (ref. 25) for the
Buckingham type potential (see Table 1). The minimization was performed by the
PENOPT-2 program (ref. 32) using a quasi-Newton method. Energy gradients were
calculated analytically.
The following restrictions and approximations were made:
(i) 'The geometries of the framework (MONO and PARA) and of the pxylene
molecules are fixed and not affected by sorption. Only the methyl groups of
pxylene are permitted to rotate freely.
(ii) No electrostatic interaction is taken into account. The pairwise summation
is performed only over the oxygen atoms of the framework, not over silicon or
aluminium sites. No cations or protons are considered, so that the interaction
with silicalite-1 rather than ZSM--5 is studied.
(iii) The zeolite framework is represented by a cut-out of the size 1.5a x 1 . 5 b
x 212, where a, b and c are the unit cell parameters. In the high-coverage
calculations the interaction of the two pxylene molecules with 16 pairs in the
neighbourhood was considered.
As previously demonstrated (refs. 8 , 2 1 , 2 2 ) the occupation of sorption sites
'TABLE 1
Potential parameters
TABLE 3
Interaction energy (kJ.mo1-I) of a single pxylene molecule with the rigid
framework at different sorption sites
MONO PARA
channel intersection -83.2 -86.6
straight channel -86.7 -91.8
sinusoidal channel -85.2 -98.5
-90-
b a c
0
0 0
0 0
-100- 0 0 0 O 0 0 0
0 0
oooooo 0 0 0
0 0
0 0 0 ooooo
I I I I I I I I I I I
Fig.1. Energy profile (see text) along the straight channel ([OlO]) at high
loading (8 mol./u.c.) beginning at the mid of the channel intersection (y/b =
0.25), minimum a: XYLla, b: XYLlb, c: XYLlc
440
Fig.?. Energy profile (see text) along the sinusoidal channel ([loo]) at high
loading ( 8 mol./u.c.) beginning at the intersection with the straight channel
(x/a = 0.5). XYLl on site XYLla ( 4 , XYLlb ( 0 ) or XYLlc (+)
4- +-h
-0-
b -0-
Fig.). High-coverage packing arrangements XYLa (left) and XYLb (right); top:
view down [OlO]; bottom: view down [OOl]; for purposes of clarity hydrogen atoms
(and at the bottom also zeolite atoms) were left out
CONCLUSIONS
'The transformation of the ZSM-5/silicalite-l framework induced by pxylene
sorption provides a considerable gain of sorption heat. A single pxylene
molecule should be able to effect in its neighbourhood a local structural change
from the monoclinic t o an orthorhombic space group. At high coverage the
sinusoidal channels are fully occupied. Inside the straight channels the
p-xylene molecules are highly mobile with respect to translation in the channel
direction. At least two distinct sites may be occupied. One of them coincides
with experimental findings.
442
TABLE 3
Fractional coordinates ( ) ( l o 4 ) of pxylene molecules for the two high-coverage
packing arrangements XYLa and XYLb
XYLla XYLlb
atom X Y Z X Y 2
XYL2a XYL2b
~-
atom X Y 2 X Y 2
ACKNOWLEDGEMENT
Part of this work was done during a stay at the Institute of Inorganic
Chemistry of the Slovak Academy of Sciences at Bratislava. The author thanks dr.
J . Noga for hospitality. Thanks are a l s o directed t o dr. J. Sauer (Berlin) for
numerous helpful discussions.
443
REFERENCES
arid G.E. Barlow, in: H.G. Karge and J. Weitkamp (Eds.), Zeolites a s
Catalvsts, Sorberits and Detergent Builders, Elsevier, Amsterdam, 1989, pp.
817-842.
38 B.F. Mentzen, in: H.G. Karge and J. Weitkamp (Eds.), Zeolites as Catalysts,
Sorbents and Detergent Builders, Elsevier, Amsterdam, 1989, pp. 477-484.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 445
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
Application of the quasi-elastic neutron scattering and NMR
pulsed field gradient technique to molecular self diffusion studies
of hydrocarbons in zeolites ZSM-5 and NaX leads to coinciding
results in both the absolute values, the concentration dependence
and activation energy of the intracrystalline self-diffusion co-
efficients. Further agreement between the neutron and NMR diffusion
data is obtained by comparing the mean molecular jump lengths which
by both techniques are found to be of the order of 1.2...0.25 nm,
slightly decreasing with increasing loading. Due to the different
time scales o f the two experimental methods applied, the mean
diffusion paths followed are of different magnitude: in neutron
scattering experiments molecular translation is measured up to 6
nm; in the NMR pulsed field gradient technique the mean molecular
displacements amount to some pm. However, in both methods, long-
range self-diffusion is detected.
INTRODUCTION
The investigation of molecular migration of sorbate and reactant
molecules in zeolites of different structures has become an impor-
tant topic in both fundamental research and industrial application.
As a most spectacular result obtained about 10 years ago, the
application of the NMR pulsed field gradient technique (cf. /1-.3/)
to the study of hydrocarbon diffusion in A type zeolites gave
evidence that for a number of systems the self-diffusion coeffi-
cients determined by the up-to-date sorption uptake methods have
been erroneous by up to five orders of magnitude /4,5/. Since this
time, the clarification of the correct order of magnitude of the
translational mobility of molecules in zeolites is one of the most
controversially discussed topics in zeolite research. The analysis
of the possible reasons for this discrepancy led to a critical
reconsideration of both the sorption measuring techniques and the
models of intracrystalline molecular transport in zeolites /6-8/.
446
EXPERIMENTAL
a) Q u a s i - e l a s t i c neutron s c a t t e r i n g
The zeolite samples were heated i n a g l a s s r e a c t o r a t 720 Y
-7
under f l o w i n g oxygen and outgassed t o a f i n a l pressure o f 10 Pa
at the same temperature. I n s i d e a glovebox, the crystals were
transferred into a slab-shaped aluminium container of circular
geometry (diameter 50 mm). The mass o f the activated zeolite
amounted t o about 5 9, thus ensuring a h i g h neutrcsn transmission.
The c e l l was connected t o a gas i n l e t system a l l o w i n g t o load the
sample w i t h the hydrocarbons a t d i f f e r e n t pressures and tempera-
t u r e s d u r i n g the neutron experiment.
The neutron r e s u l t s were obtained a t the I n s t i t u t Laue-Langevin,
Grenoble, using t h e t i m e - o f - f l i g h t spectrometer IN5 w i t h incident
wavelengths o f 0.8 and 0.9 nm and e l a s t i c r e s o l u t i o n s o f ca. 25
and 1 9 peV, respectively. Because o f the l a r g e incoherent cross
section o f hydrogen, the s c a t t e r i n g from hydrocarbon molecules i s
largely incoherent. The coherent S c a t t e r i n g from the zeolite is
avoided as much as p o s s i b l e by t a k i n g s e l e c t e d groupings of the
d e t e c t o r s between t h e Bragq peaks o f t h e z e o l i t e .
THEORY
a) Quasi-elastic neutron scattering
The long-range translational motion of a molecule can be derived
from the broadening of the elastic peak a s a function of the momen-
tum transfer. For hydrocarbons in zeolites, only incoherent scatte-
ring has to be considered because of the large incoherent cross
section of hydrogen. The intensity scattered by the sample i s then
proportional to the incoherent scattering law Sinc(Q,o), which i s
related to the self-motion of protons (-0 and nu denote t h e neutron
momentum transfer and the neutron energy transfer, respectively).
The broadening values obtained for methane diffusing in zeolites
can be fitted to a model of a diffusion process proceeding via
molecular jumps with a Gaussian distribution of j u m p lengths / 2 0 / .
Thus, the scattering law becomes a Lorentzian,
S(Q,o) = _1_ .
&(Q)
n w2 + CaO(Q)12 '
whose half-width at half maximum (HWHM)
This model w a s used for ethane and benzene in NaX because the
broadening curves converged more slowly towards their asymptotic
values at high Q than for methane in NaZSM-5.
RESULTS
a ) Methane d i f f u s i o n i n ZSM-5
The results obtained i n the QENS f o r t h e broadening of the
elastic peak versus Q2 a t 200 K a r e shown i n F i g . 1 for different
loadings.
Fig. 1
Elastic peak broadening versus GI2
for CH i n ZSM-5 a t 2OOK for the
loadings
8 CH4 per U.C.
(A)
2, ( I4, )and (v)
I t f o l l o w 5 from Fig.1 t h a t i n the
QENS experiments the broadening of
2
the e l a s t i c peak as a f u n c t i o n o f Q
deviates from a straight line so
that a jump d i f f u s i o n model w i t h a
Gaussian distribution o f the jump
l e n g t h s has t o be considered. This
interpretation i m p l i e s t h a t molecu-
l a r jumps w i t h v a r y i n g jump lengths
may occur w i t h i n t h e channel seg-
ments a s w e l l as across the indi-
vidual channel intersections. The
s e l f - d i f f u s i o n c o e f f i c i e n t s obtained
a r e presented i n Table 1.
Fig.2
Spin echo attenuations d u e
100 to intracrystalline self-
80 diffusion of CH4 in NaZSM-5
m
60 at 250 K for the loadings
c
C ( 0 ) 4 ; (.)8and ( 0 )
-=!a 12 molecules per u.c., re-
2
.-.
* spectively. For calibration,
the echo attenuations for
I *O neat water (
ammonia (A v
) ,
) and liquid
whose self-
10 diffusion coefficients taken
1 3 4 5 6 7 8 9 10
-2 $ g 2 6 * ( A - + & I / re\.units
from literature amount t o
2.3 x loF5 cm2s-' /23/ and
1.5 x cm2s-' /24/,
respectively, are included.
450
CH4iu. c . D ~ ~ D ~ ~ ~~ /~ D / ~ ~ D~ ~ ~ ~ /~ /
<: 1 0 ~ ~ ~ ~ . - ~ x 1o5cm2s-'
1.5 5.0
2 2.8
2.8 5.9
4 2.5 3.7 6.3
8 2.9 2.8 5.2
12 2.5 4.5
Frg.3
Energy spectra for
ethane in NaX at
different Q values
-
3
(253 K-, 4.3 CZH6
p e r supercage) .
-.
0'
- 0 4 -02 0 02 04 06 08 hw(meV)
I Fig .4
Comparison of the self-dif-
, fusion coefficients of
ethane in NaX at 253 K mea-
sured by QENS ( A this
study) and the NMR PFGT
,1261)-
1
(
‘“:I
.“-5!
1
,
2 3
,
4
, ,
5
n
6 7
loading/ D/ <12>1/2/ T/
6 2 -1
C6H6 per supercage x 1 0 cm s nm x 1d1s
Fig. 5
Comparison of the self-
diffusion coefficients of
N
benzene i n NaX a t 458 K
5
\
directly determined by b o t h
n the NMH PFGT ( 0 0 / 3 3 / and
10-6 /28/) and QENS ( A , / 1 3 / )
n with the corresponding d i f -
0 fusivities determined
non-equilibrium measurements
piezometric/30/;
from
+,
10.~ :e?b 'Length Column method
/32/;n,frequency response
and s i n g l e s t e p frequency
response technique /31f-.) as
w e l l as deduced from NMH
10-8 l i n e shape a n a l y s i s ./rS4/.
The r e g i o n o f the r e s u l t s o f
gravimetric measurements
with different specimens
/28/ is indicated by a
10-9 hatched area. Asterisked
0 1 2 3 1 5 symbols represent data which
Loading / C6H6 per supercoge have been obtained by e x t r a -
p o l a t i o n from lower tempera-
tures.
DISCUSSION
B o t h QENS and NMR PFGT, a r e methods enabling t h e investigation
o f molecular self-diffusion, i.e. t h e n e t effect o f a succession o f
consecutive elementary s t e p s o f m a s s transfer a t sorption equili-
brium. However, d u e to the different t i m e s c a l e s o f t h e t w o
methods, the mean diffusion paths followed a r e o f different magni-
tude: while in QENS, molecular translation i s measured u p t o 6 nm,
in NMR P F G T t h e mean molecular displacements may amount t o several
pm. Nevertheless, for t h e three adsorbate-adsorbent s y s t e m s under
study, the self-diffusion coefficients measured independently by
neutron scattering and NMR a r e in very good agreement.
However, in the c a s e o f the methane diffusion in ZSM-5, the
self-diffusion coefficients given in T a b l e 1 a r e by about s i x
o r d e r s of magnitude larger than t h o s e determined by gas-chromato-
graphy /35/, t w o o r d e r s of magnitude larger than t h e diffusion
coefficients determined by using a permeation method with a zeolite
membrane /36/ and by a factor o f 5 larger than diffusion coeffi-
c i e n t s measured by means of t h e frequency-response s i n g l e s t e p
analysis Ill/. Also for t h e benzene diffusion in NaX, d i f f e r e n c e s
of t w o o r d e r s of magnitude a r e still open f o r explanation / l O / -
T h e s e strong differences cannot be explained by theory. Following
the formalism o f irreversible thermodynamics, t h e diffusion coeffi-
cient determined under non-equilibrium sorption c o n d i t i o n s should
be expected t o be either equal ( i n t h e c a s e o f a linear sorption
isotherm, Henry's law) o r larger ( f o r convex shaped isotherms s u c h
a s those o f t h e Langmuir type) than t h e self-diffusion coefficient
measured at sorption equilibrium /37/. While in t h e Q E N S and NMR
P F G T experiments intrinsic intracrystalline self-diffusivities are
measured, diffusion coefficients derived from adsorption/desorption
experiments can be affected, additionally, by intercrystalline
diffusion (bed d e p t h ) influences, sorption heat release processes
and/or by transport resistances near t h e crystal s u r f a c e ( s u r f a c e
barriers).
CDNCLUSIUNS
(1) T h e joint application of Q E N S and NMR PFGT t o t h e adsorbate-
adsorbent s y s t e m s CH4/NaZSM-5. C2H6/Nal( and C6H6/NaX leads t o
coinciding results in both t h e absolute values o f t h e intra-
crystalline self-diffusion coefficients, their concentration
dependence, t h e e n e r g i e s o f activation o f self-diffusion, t h e
mean molecular j u m p lengths and t h e correlation t i m e s o f
molecular motions.
454
ACKNOWLEDGEMENT
The authors thank Dr. G . J . Kearley (Grenoble) f o r his help in
performing the neutron experiments at the Institut Laue-Langevin
Grenoble and Dr. W . Heink (Leipzig) for the development of the NMR
spectrometer FEGHIS.
455
LITERATURE
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Zeolites, Reno, 1983, Butherworths, 1984, p,104.
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Z. Chem., 2 1 (1981) 175.
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J. Phys. Chem, 90 (1986) 1059.
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1191 C.J. Wright and C. Riekel, Molec. Phys. 36 (1978) 695.
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Z. phys. Chemie (Leipzig), 269 (1988) 1101.
1231 H. Weingartner, Z. phys. Chemie, N.F., 132 (1982) 129.
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Transportphanomene I, p.583, Springer Verlag Berlin, 1969.
/25/ J. Caro, M. Biilow, W. Schirmer, J. Karger, W . Heink, H.
Pfeifer and S.P. rdanov,
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J. Chem. S O C . , Faraday Trans. I, 76 (1980) 717,".
1271 M. Bulow, J. Karger, M. KoEiFik and A. M. Voloscuk,
Z. Chem., 2 1 (1981) 175.
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J. Chem. S o c . , Faraday Trans. I, 77 (1981) 1485.
/29/ N.6. Van-Den-Begin and L.V.C. Rees, in "Zeolites:Facts,
Figures, Future", eds. P.A. Jacobs and R.A. van Santen,
Elsevier, Amsterdam, 1989, p. 915.
/ S O / M. Bulow, W . Mietk, P. Struve and P. Lorenz,
J. Chem. S O C . , Faraday Trans. I, 79 (1983) 2457.
/31/ Dongmin Shen and L.V.C. Rees, unpublished results.
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S.P. tdanov, Zeolites, 5 (1985) 91.
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Processes, Wiley-Interscience Publ., New York, 1984.
This Page Intentionally Left Blank
G.Ohlrnann et al. (Editors), Catalysis and Adsorption by Zeolites 457
1991 Elsevier Science PublishersB.V.. Amsterdam
E.R. Geusl, A.E. Jansen', J.C. Jansen', J. Schoonmanl, and H. van Bekkum'
Delft University of Technology, Laboratory of Applied Chemistry,
Julianalaan 136, 2628 BL Delft, The Netherlands
TNO-MT, Utrechtseweg 48, 3704 HE Zeist, The Netherlands
SUMMARY
Permeation experiments on large silicalite single crystals (MFI type),
embedded in an epoxy resin were performed, using permanent gases and small
alkanes. A scaling-up from initially a one zeolite crystal membrane to a
multi zeolite crystal membrane is presented. Differences in permeability were
small and attributed to a sorption-diffusion mechanism, in qualitative
agreement with theory. As permeation may vary within different regimes,
maximum selectivities are expected in the Henry region. Some boundary
conditions in the preparation of (ceramic) zeolite membranes are formulated.
INTRODUCTION
Zeolite membranes may open new horizons in both separation technology and
reaction engineering. At present, most gas separation membrane processes are
operated using polymer membranes. Ceramic membranes can be used at higher
temperatures, which allows regeneration and catalytic application (ref. 1).
The sol-gel technique has been used successfully in the preparation of
ceramic membranes (refs. 2-5). Alumina gas separation membranes can be
produced on a semi-industrial scale with relative ease (ref. 6). Zeolite
membranes in an all-ceramic system are expected to exhibit significantly
higher selectivities due to the zeolite's molecular sieve characteristics.
In the development and use of zeolite membranes it is essential to obtain
information on the mass transport through zeolite crystals. Recently an
extensive mathematical model for the permeation through porous crystal
membranes has been proposed by Barrer (ref. 7).
In the experimental field Hayhurst and Paravar (refs. 8 - 9 ) reported on the
determination of the diffusivity of alkanes by means of a zeolite membrane
configuration. These experiments, however, were performed on a twinned
silicalite crystal at low feed pressures. Recently this work was extended by
similar experiments on benzene passage through a silicalite single crystal
(ref. 10). Wernick and Osterhuber (refs. 11-12) reported on the permeation
through a NaX single crystal. Significantly higher feed pressures were used
in these experiments, and the permeation characteristics in time were
emphasized.
According to patent literature ceramic zeolite membranes have been prepared
by crystallizing zeolites in situ either in (ref. 13), or on (refs. 14-18) a
macroporous support. Alternatively, small zeolite crystallites together with
458
THEORY
Barrer (ref. 7) recently proposed a permeation model for systems obeying
Langmuir's isotherm in which activated intracrystalline diffusion takes
place. In addition external surface effects on both feed and permeate side
were included, resulting in a five step process. In this work we will focus
on the overall permeability, which is expected to be governed by a sorption-
diffusion mechanism.
A convenient way to define the permeation rate of a membrane makes use of
the permeability ( @ ) (ref. 23). which can be derived from Fick's first law of
diffusion:
in which Qmor denotes the steady state flow, A,,, the surface area of the
membrane, 1, the membrane thickness (in this work the crystal size in the b-
direction), and Ap the pressure difference over the membrane. The
permeability should be considered a phenomenological parameter of the
membrane, resulting from specific conditions (i.e. pressure, temperature,
feed composition, degree of fouling). Formula [l] will be used to calculate
the permeability from the permeation rate at steady state.
According to Barrer's model, maximum permeation will occur when the mass
transport is only governed by intracrystalline diffusion. This holds if
sorption processes on both sides of the membrane are much faster than
459
intracrystalline diffusion:
'mo1,max Dintra,diff * %
/
'
m *
I --
in which Acmax denotes the maximum concentration difference over the
membrane. Acmax can be derived from sorption isotherms (assuming equilibrium
between gas and adsorbed phase). Dintra,diff can be obtained from NMR data,
referring to the intracrystalline self-diffusivity (Dself). The PFG NMR
technique measures DSelf directly, albeit only for rapid processes (ref. 2 4 ) .
The Darken equation enables one to calculate the intracrystalline Fickian
diffusivity (ref. 2 5 ) :
Dintra,diff = Dself *
For the Langmuir isotherm, equation [ 3 ] may be written as:
in which 6' denotes the fraction of sites occupied. NMR results (ref. 2 6 ) have
shown that for small alkanes (C1-C3) DSelf decreases for increasing carbon
number, due to the diminished molecular free volume. For sufficiently high 6'.
this effect is overruled by the increase of 1/(1 - 6') (ref. 2 5 ) .
During permeation a concentration profile will exist over the zeolite
crystals, which will remain constant at steady state. As 6' varies over the
membrane, an average diffusivity can be found by integrating over the total
membrane. Finally, equation [ 2 ] is rewritten as:
When 6' is high over the whole membrane, the Fickian Dintra,diff will be
significantly higher than the NMR DSelf. Thus, the sorption equilibrium will
influence the permeability of a species, and both sorption and diffusion
should be considered in evaluating the permeability through a zeolite
membrane.
EXPERIMENTAL
Large. flat silicalite single crystals were synthesized as described by
Jansen et al. (ref. 2 7 ) . The Si/Al ratio (> 3 0 0 ) was determined by ICP
analysis on large crystals from a single batch. Selected crystals of about
equal size (a.b,c = 200*100*350 p n ) were carefully calcined at 500' C
(heating rate 1" C/min).
In a preliminary experiment one large silicalite crystal was mounted in an
epoxy resin film (bisphenol A glycidyl ether/poly amine; Araldit, Ciba-
Geigy). As this procedure was rather time consuming and complex, a more
460
RESULTS
Some preliminary experiments were performed as to make sure that only
transport through the zeolite crystals was to take place. To double check,
experiments were carried out several times, using different membranes.
The non-permeability of the epoxy resin was checked by membrane M1. Up to
200" C no permeation could be detected, establishing that the epoxy resin
meets the requirements.
On an as-synthesized crystal (still containing the template molecules;
membrane Cl), embedded in a similar way, no permeation could be detected. The
expected permeation rate (related from measurements on LPZ-3b at similar
conditions) should have been significantly higher than the accuracy of the
apparatus. Thus, it was concluded that zeolite crystals could be embedded
properly by means of the present procedure.
Membrane MES-21 is the initial one crystal composite. For all gases very
high permeabilities were found (cf. Table 2 ) . resulting in Knudsen diffusion
selectivity. Inspection by scanning electron microscopy revealed a large
crack in the zeolite crystal. The high permeability and Knudsen selectivity
are attributed to the presence of this crack.
Permeation results on membrane LPZ-1 are listed in Table 2 as well. The
permeability for each gas seemed to increase slightly after repeated
experiments. For this reason LPZ-1 was removed from the cell for inspection.
Two out of ten crystals appeared to be cracked, and subsequently these
crystals were completely covered by fresh epoxy resin.
Permeation rates through the thus repaired membrane (LPZ-3; Figure 3) were
462
nearly two orders of magnitude lower than for LPZ-1 (cf. Table 2). This
change in permeability can not be accounted for by the loss of free surface
area, which is only 20%. It can be seen from Table 2 that no high
selectivities for the various gases were found. The permeability for n-
butane at 30" C (LPZ-3a) was higher than for other gases tested.
T ('C) 25 30 30 130 30
AP (bar) 1-2 1.6-1.8 1.6 1.6 1.6
Gas
found that some crystals were cracked, so the increased permeability is not
an effect of the activation at higher temperature.
During the first few experiments on LPZ-3a (at 30' C) the zeolite pores
proved to be obstructed by adsorbed vater. FTIR-spectra (Figure 4) of
calcined silicalite crystals reveal a considerable amount of adsorbed vater
under ambient conditions. As the phenomenon vanished after some experiments,
the adsorbed water is apparently induced to desorb by the permeating gas.
1.8
I . 35
0.9
0. a 5
0.e 4 I t
4000 3528 3000 z m 2000 ism iaaa
YAVENUMBERS C H - 1
DISCUSSION
In Table 3 the calculation of the maximum flow according to equation [5] is
shown for the linear alkanes C1-C4 at 30", assuming a linear concentration
profile. Unfortunately, the required data on sorption (ref. 29) and diffusion
(ref. 26) were rather incomplete. The effect of sorption on DFickaV is only
demonstrated qualitatively.
TABLE 3: Maximum theoretical flows of linear alkanes C1-C4 for membrane LPZ-
3 , calculated from equation [ 5 ]
')fract .ion of sites occupied on feed (F) and permeate (P) side (equilibrium)
$ ) data extrapolated from sorption data (ref. 29). cf. text
I)data extrapolated from diffusion data (ref. 26), cf. text
The intracrystalline self-diffusivity of n-butane can not be determined by
the PFG NMR technique (ref. 30). and was estimated from data on methane,
ethane, and propane. The correlation of the intracrystalline diffusivity to
the carbon number for n-alkanes, found by Eic and Ruthven with the ZLC method
(ref. 30) was used. The sorption data on methane were estimated from sorption
isotherms of ethane, propane, and n-butane (ref. 29).
Because of lack of sufficient data, permeabilities of permanent gases (H2,
N2, and 02) and carbon dioxide were not calculated. The sorption behaviour of
nitrogen and to a lesser extent carbon dioxide has been shown (ref. 31) to
obey Henry's law up to high temperatures (70" C), and high pressures (up to 1
bar). In contrast to the alkanes, no sorption effect is expected for
permanent gases, as (aln p/aln c) remains constant.
In contrast to theory (Table 3), small differences in permeability are
measured (Table 2 ) . Permeabilities are considerably smaller (methane, ethane)
than the maximum flows, or of the same magnitude (n-butane) . This implicates
that other processes (e.g. sorption to and from the zeolite pores) than
intracrystalline diffusion govern the permeation.
Applying l o w feed pressures (up to 1.8 kPa), Hayhurst and Paravar have
found high selectivities (ref. 9). In their experiments however, permeation
occurred through the c-direction (ref. 32). resulting in a high tortuosity
factor. Permeation may therefore be hindered, especially for higher alkanes.
Negligible selectivity was also found by Wernick and Osterhuber (ref. 11)
on binary and ternary mixtures of various alkanes (NaX crystal). The reported
465
rapid and slow permeation regime transition may be (partly) explained by the
sorption effect on intracrystalline diffusion, as high feed pressures (1 bar)
were applied (permeate pressure < 133 Pa). In the rapid permeation regime the
factor (aln p/ah c) will be high, due to high site occupation. This rapid
regime was found to be metastable for higher temperatures (65°-1000 C).
Sorption experiments by Stach et al. (ref. 33) have shown that sorption on
permeate side (13.3-133 Pa) decreases strongly in this temperature region.
From these studies it is concluded that the highest selectivities will be
realized in the Henry regime. Table 3 indicates that at equal conditions the
difference between DSelfmaX and DFickaV will be larger for higher alkanes. As
sorption is small in the Henry region, the permeation is governed by the
intrinsic diffusivity only. In order to achieve high permeabilities, the
Henry regime is favourably reached by an increase of temperature.
CONCLUSION
Large silicalite single crystals have been found to be permeable for
permanent gases and small alkanes. A scaling-up of the mass transfer was
achieved by embedding several zeolite crystals into one membrane.
Permeation through zeolite membranes may occur within different regimes.
Maximum selectivity is expected to be realized in the Henry region, in which
the intracrystalline diffusivity is hardly affected by sorption.
The application of large zeolite crystals in preparing zeolite membranes is
to be preferred from a preparative point of view. Draw-backs, however, may be
the sensitivity to high feed pressures, and relatively low permeabilities. As
zeolite membranes have to be (re)-activated, all-ceramic membrane
configurations are strongly recommended.
ACKNOWLEDGEMENT
E.R. Geus is very grateful to Prof. R.M. Barrer for a stimulating
discussion on zeolites as membranes.
REFERENCES
H.P. Hsieh, Inorganic Membrane Reactors - A Review, AIChE Symposium Series
5 , 8 5 , no. 268, (1989), 53-67;
A. Larbot, A. Julbe, C. Guizard, L . Cot, J.Membr.Sci., 93, (1989), 289-
303 ;
A. Larbot, J.P. Fabre, C. Guizard. L. Cot, J.Am.Ceram.Soc., 72, (1989),
257-61;
W.A. Zeltner, M.A. Anderson, ‘Chemical Control over Ceramic Membrane
Processing: Promises, Problems and Prospects’, in: Proc. 1st
Int.Conf.Inorg.Membr., (eds. J. Charpin, L . Cot), Montpellier, France,
July 3-6, 1989, 213-223;
A. Leenaars, Preparation, Structure and Separation Characteristics of
Ceramic Alumina Membranes, thesis, University of Twente, Netherlands,
(1984) ;
H.M. van Veen, R.A. Terpstra, J.P.B.M. Tol, H.J. Veringa, ’Three-Layer
Ceramic Alumina Membrane for High Temperature Gas Separation
Applications’, in: Proc. 1st Int.Conf.Inorg.Membr., (eds. J. Charpin, L.
Cot), Montpellier, France July 3-6, 1989, 329-335;
466
SUMMARY
The a d s o r p t i v e d i f f u s i v i t y o f 2,3-dimethylbutane (2,3-DMB) i n s i l i c a l i t e
(373-473 K) o b t a i n e d by t h e v o l u m e t r i c method has been compared w i t h t h a t
o b t a i n e d f ro m c r a c k i n g r e a c t i o n s o v e r l a r g e aluminat ed s i l i c a l i t e c r y s t a l s
(673-773 K) i n a f i x e d - b e d c o n t i n u o u s - f l o w r e a c t o r .
A n a l y s i s o f 2,3-dimethylbutane c r a c k i n g r a t e s w i t h T h i e l e ’ s model r e s u l t s i n
experiment a l r e a c t i o n e f f e c t i v e n e s s f a c t o r s which a r e c l o s e l y f o l l o w e d by
t h e o r y . The a c t i v a t i o n energy o f t h e r e a c t i o n l i m i t i n g d i f f u s i v i t y o f 2,3-
di met h y lbut a ne i n aluminated s i l i c a l i t e i s found t o be much h i g h e r t h a n t h e
a c t i v a t i o n energy o f t h e c o r r e s p o n d i n g a d s o r p t i v e d i f f u s i v i t y . T h i s phenomenon
i s shown t o be c h a r a c t e r i s t i c f o r t h e c a t a l y s t sample.
INTRODUCTION
D e s p i t e numerous i n v e s t i g a t i o n s t o d e t e r m i ne i n t r i n s i c and s e l f - d i f f u s i v i t i e s
o f adsorbates i n z e o l i t e channels and c a v i t i e s , e s t i m a t i o n s o f t hese parameters
from catalytic experiments ( a t h i g h t e m p erat ures) a r e scarce (1,Z). It i s o f
high interest to compare diffusion data determined under i n e r t c o n d i t i o n s
(adsorptive d i f f u s i v i t i e s ) w i t h t h e s e ‘ c a t a l y t i c ’ d i f f u s i v i t i e s . As i t i s n o t
p o s s i b l e t o do b o t h t y p e s o f experiments a t t h e same t emperat ure, comparison
can o n l y be made t h r o u g h t h e a c t i v a t i o n energy o f d i f f u s i o n , assuming t h a t t h e
ze ol it i c d i f f u s i v i t y i n c r e a s e s exponenti a1 l y w i t h temperature.
Zeolite ZSM-5 offers an attractive o p p o r t u n i t y t o compare c a t a l y t i c and
adsorptive d i f f u s i o n r a t e s o f hydrocarbons, f o r i t i s a h i g h l y a c t i v e c a t a l y s t
and can be synthesised i n crystals large enough f o r a d s o r p t i v e d i f f u s i o n
experiments ( 3 ) . U n f o r t u n a t e l y , d i r e c t l y s y n t hesised ZSM-5 c r y s t a l s i n v a r i a b l y
have been found c o n t a i n more aluminium a t t h e i r r i m t h a n a t t h e i r core.
to
Since such a aluminium g r a d i e n t and i t s c o n comit ant heterogeneous d i s t r i b u t i o n
in catalytically active s i t e s impedes t h e successf ul a p p l i c a t i o n o f T h i e l e ’ s
t h e o r y t o ’ c a t a l y t i c ’ d i f f u s i o n , h e r e we r e p o r t on l a r g e ZSM-5 c r y s t a l s
o b t a i n e d by a l u m i n a t i o n o f p u r e l y s i l i c e o u s ZSM-5 frameworks ( s i l i c a l i t e ) . 2,3-
Dimethylbutane i s used as probe molecule because i t ’ s k i n e t i c d i a m e t e r i s
comparable t o t h a t o f t h e ZSM-5 channels and t h u s w i l l r e n d e r e x t e r n a l h e a t and
m a s s - t r a n s f e r r e s i s t a n c e n e g l i g i b l e i n a d s o r p t i v e methods.
468
EXPERIMENTAL
D i r e c t s v n t h e s i s and c h a r a c t e r i s a t i o n o f s i l i c a l i t e and o f ZSM-5
Two batches o f l a r g e s i l i c a l i t e c r y s t a l s ( S i l l and Si12) were prepared
by an a l k a l i n e - f r e e s y n t h e s i s method o f Ghamami e t a l . ( 5 ) . A t h i r d s i l i c a l i t e
sample (Si13) was s y n t h e s i s e d a c c o r d i n g t o p a t e n t l i t e r a t u r e ( 6 ) . Elemental,
s t r u c t u r a l and a d s o r p t i v e c h a r a c t e r i s a t i o n methods as w e l l as methods t o
de t ermine c r y s t a l morphologies and c r y s t a l s i z e d i s t r i b u t i o n s have p r e v i o u s l y
been d e s c r i b e d ( 3 ) .
I n T a ble 1 a summary o f t h e samples’ c h a r a c t e r i s t i c s i s g i v e n . S i l i c a l i t e was
dealuminated w i t h H20/HC1 a t 1073 K a c c o r d i n g t o a st andard method (7), l e a d i n g
to samples S i l l d , S i l L d and S i l 3 d . X - r a y powder d i f f r a c t i o n (XRD) and i n f r a r e d
spectroscopy (IR) showed that the p a r t i a l dealumination d i d n o t a f f e c t the
crystallinity o f t h e samples. Dealuminated samples were used i n t h e a d s o r p t i v e
d i f f u s i o n experiments.
TABLE 1
C h a r a c t e r i s a t i o n o f (dealuminated) s i l i c a l i t e samples
Mean c r y s t a l l e n g t h ,
c - d i r e c t i o n (pm) 34.9 89.3 5&
Mean c r y s t a1 he ig ht
#
a- o r b - d i r e c t i o n (pm) 11.4, 8 . 4 39.7
S i 1 i c o n - t o - a 1 umi n i um r a t i o6 503/600* 400/ 500* 150/400*
Occurrence o f c r y s t a l
agglomerates r10 Yes Yes
n-Hexane ads. (wt%) 10.09/10.19* 10.75/10.72* 10.66/10.83*
A1 umination o f s i l i c a l it e
S i l i c a l i t e S i l l and Si12 were aluminated a t 773 K w i t h A1C13 according t o
Yamagishi e t a l . (9), followed by a repeated ammonium exchange. The aluminated
samples are denoted S i l A l l and SilA12, r e s p e c t i v e l y .
The aluminium d i s t r i b u t i o n in SilA12 c r y s t a l s was determined by Electron-
Probe Microanalysis (EPMA) .
AdsorDtive d i f f u s i o n and adsorDtion constants
The d i f f u s i v i t y o f 2,3-dimethylbutane (2,3-DMB) i n t h e s i l i c a l i t e samples was
determined i n a constant volume v a r i a b l e pressure system as described e a r l i e r
(10)-
The experimental parameters of diffusion measurements performed w i t h
Silld and S i l 2 d were: pressure = 50 - 700 Pa a t 373 K and 1000 - 10000 Pa a t
473 K; amount sorbed = 1.3*10-3 - 7*10-3 mmol/g per uptake run a t both
temperatures. Adsorption c a p a c i t i e s were 0.60 and 0.24 mmol/g a t 373 K and 473
K, respectively. I n addition 2,3-DMB adsorption isotherms were obtained on
silicalite Sil3d at
373, 473 and 523 K. Adsorption data on S i l 3 d above 673 K
were determined by gas chromatography as described e a r l i e r (3).
Catalvsis
Cracking reactions were performed in a fixed-bed continuous f l o w glass
microreactor, (3), w i t h 6% 2,3-DMB (>99 %), 6% 3-methylpentane (>99.5%) o r 2%
n-butane (>99.5 %) i n d r y helium a t 101 kPa. The products o f t h e cracking
reactions were gaschromatographical l y analysed.
Apparent first order r a t e constants, kaPP, were determined according t o
conventional equations (3).
A1 uminat i o n
Alumination of Sill and Si12 has r e s u l t e d i n a s u b s t a n t i a l increase o f the
aluminium content (Table 2) whereas t h e adsorptive p r o p e r t i e s f o r n-hexane have
remained unchanged. Results of the elemental analysis reveal
TABLE 2
Characterisation o f aluminated s i l i c a l i t e samples
Adsorot ive d i f f u s i on
An analysis o f adsorption isotherms o f 2,3-DMB revealed t h a t t h e r e are no
serious deviations in adsorptive p r o p e r t i e s o f t h e (dealuminated) s i l i c a l i t e
samples. Thus a comparison of data on diffusion obtained w i t h d i f f e r e n t
adsorbent samples i s j u s t i f i e d as the adsorption c h a r a c t e r i s t i c s are comparable
f o r each sample.
In Figures 2 and 3 uptake curves are shown f o r 2,3-DMB d i f f u s i o n a t low
coverage (maximum 3.5 molec. 2,3-DMB/u.c.) i n a volumetric system a t 373 K and
471
--: 5 0 0 0 .
L A
SI
4000
.r
b %
c
3000. Al
10'/T, K"
b-dlractlon (mlcron)
r;
1.0'I 1.0
Y Y
0.8 0.8
I
0.6 0.6
0.4 0.4
0.2 0.2
*
0.0 1 J 0.0 4
0 100 200 300 400 0 1000 2000 3000
t,
473 K , respectively. It is clear that the theoretical curve follows the data
reasonably well up to high relative uptake.
TABLE 3
Apparent and intrinsic diffusivity of 2,3-DMB in dealuminated silicalite
samples Silld and Sil2d at 373 K and 473 K
’Catalytic’ diffusion
First order rate constants have been determined for the 2,3-DMB cracking
reaction over the directly synthesised H-ZSM-5 sample and over the aluminated
silicalite samples SilAll and SilA12. The rate constants relate t o steady state
situations. Figure 4 shows an Arrhenius plot revealing that the apparent
activation energy of reaction is highly dependent on the size o f the zeolite
473
c r y s t a l s . I f t h e c o n c e n t r a t i o n s o f a c t i v e s i t e s i n t h e d i f f e r e n t samples do n o t
diverge t o a l a r g e e x t e n t t h i s phenomenon i s i n d i c a t i v e o f a r e a c t i o n which i s
l i m i t e d by the diffusional r a t e o f r e a c t a n t and/or p r o d u c t molecules i n t h e
zeolite channels. As 2,3-DMB i s a f a r more b u l k i e r molecule t h a n i t s c r a c k i n g
pro duc t s i t i s presumed t h a t t h e r e a c t i o n i s l i m i t e d by r e a c t a n t d i f f u s i o n . The
r e a c t i o n ov er t h e ZSM-5 sample has t h e h i g h e s t a c t i v a t i o n energy o f w e l l over
100 kJ/mole. T h i s i s i n d i c a t i v e o f a c o n v e r sion n o t l i m i t e d by i n t r a c r y s t a l l i n e
2,3-DMB d i f f u s i o n .
The use o f t h e Thiele theory i n determining t h e d i f f u s i v i t y o f t h e reactant
requires knowledge o f t h e i n t r i n s i c a c t i v i t i e s o f t h e z e o l i t e samples. We have
determined intrinsic activities by employing a reference reaction, viz. n-
butane c r a c k i n g . T h i s r e a c t i o n i s expected t o occur w i t h o u t any i n t e r f e r e n c e o f
diffusion i n t h e ZSM-5 c r y s t a l s because t h e k i n e t i c d i a m e t e r o f n-but ane ( 0 . 4 9
nm) i s l o w e r t h a n t h a t o f 2,3-DMB (0.56 nm).
F i r s t o r d e r r a t e c o n s t a n t s f o r t h e n-butane c r a c k i n g r e a c t i o n over t h e H-ZSM-
5 sample and ov e r t h e a l u m i n a t e d s i l i c a l i t e s a r e again present ed i n t h e f orm o f
an A r r h e n i u s p l o t i n F i g u r e 5. From t h e r e s p e c t i v e a c t i v a t i o n e n e r g i e s i t can
be concluded t h a t a l l c o n v e r s i o n s o c c u r w i t h an e f f e c t i v e n e s s f a c t o r (0) equal
to unity and that the cracking rate is therefore not retarded by
i n t r a c r y s t a l l i n e n-butane d i f f u s i o n .
I f t h e c a t a l y s t p a r t i c l e i s c o n s i d e r e d t o be o f p l a t e geometry, permeable f o r
reactant molecules i n one direction only, the effectiveness factor is
t h e o r e t i c a l l y g i v e n by:
4 i s t h e T h i e l e modulus:
TABLE 4
Reaction l i m i t i n g d i f f u s i v i t i e s o f 2,3-DMB i n aluminated s i l i c a l i t e .
1=723 K
-4 D,~'K, = 7.3. m2/s
k. s-'
1.00
0.10
P
1=773 K
0.0 1
1.2 1.4 1.6 DeffK, = 1 . 2 6 lo-'' m 2 / s
lO'/T, K-'
Fig. 5:
Def f
10-14
10-15
.. 1
I -
a d s o r p t i v e d i f f u s i v i t i e s t o l o w e r r e c i p r o c a l t emperat ures i s w i t h i n an o r d e r o f
magnitude. However, t h e a c t i v a t i o n e n e r g i e s o f d i f f u s i o n , ED, d e v i a t e , v i z . 121
kJ/mole f o r t h e ' c a t a l y t i c ' and 52 kJ/mole f o r t h e a d s o r p t i v e d i f f u s i v i t y .
I n o r d e r t o f i n d o u t whether t h i s d e v i a t i o n o r i g i n a t e s f r o m t h e p r o p e r t i e s o f
t h e r e a c t a n t molecule, 2,3-DMB, o r t h e c a t a l y s t , we have repeat ed t h e c r a c k i n g
experiments u s i n g 3-methylpentane. U s i n g d i r e c t l y s y n t h e s i s e d l a r g e ZSM-5
crystals we have determined d i f f u s i v i t i e s a t 723 K and a t 811 K which, a f t e r
extrapolation, corresponded satisfactorily with 1 ow-temperature adsorptive
d i f f u s i v i t i e s (3).
An Arrhenius plot of t h e r e s u l t s ( F i g . 8) shows t h a t , c o n t r a r y t o 2,3-DMB
cracking, the 3-methylpentane conversion is diffusion l i m i t e d o v e r sample
S ilA 12 only. Using the same method as i n t h e 2,3-DMB case t h e ' c a t a l y t i c '
d i f f u s i v i t y o f 3-methylpentane i n a l u m i n a t ed s i l i c a l i t e has been determined.
A d s o r p t i o n d a t a r e p o r t e d e a r l i e r ( 3 ) have been used t o c a l c u l a t e t h e t r u e Deff
from Deff*Kc. I n Table 5 t h e r e s u l t s o f t h e e s t i m a t i o n s a r e compared w i t h d a t a
TABLE 5
Reac t io n l i m i t i n g d i f f u s i v i t i e s o f 3-methylpentane i n aluminat ed s i l i c a l i t e and
i n ZSM-5. Data on ZSM-5 and a d s o r p t i o n c o n s t a n t s a r e t a k e n f r o m r e f . 3.
CONCLUSIONS
I n t h i s study 2,3-DMB has been chosen as probe hydrocarbon species i n
d i f f u s i o n experiments w i t h (aluminated) s i l i c a l i t e c r y s t a l s . The uptake o f t h i s
compound in adsorption experiments at 373 K and a t 473 K was c o n t r o l l e d by
i n t r a c r y s t a l line diffusion, not influenced by external heat and/or mass
t r a n s f e r resistances.
Cracking experiments were performed w i t h t h e probe hydrocarbon a t 673-773 K
using large crystals of aluminated s i l i c a l i t e . Reactions were l i m i t e d by
intracrystalline diffusion o f 2,3-DMB. It was found that aluminium was
deposited randomly through a large silicalite crystal. Also an n-butane
cracking activity of aluminated silicalite equal to that of directly
synthesised H-ZSM-5 ( o f comparable s i l i c o n - t o - a l u m i n i u m r a t i o ) was found. As
the a c t i v e s i t e s were d i s t r i b u t e d homogeneously throughout t h e z e o l i t e c r y s t a l
the rates o f diffusion and o f r e a c t i o n were equal a t any l o c a t i o n w i t h i n a
crystal. Therefore an important condition for using Thiele’s model i n i t s
simple form was f u l f i l l e d . ’ C a t a l y t i c ’ d i f f u s i v i t i e s were estimated between 673
K and 713 K.
478
ACKNOWLEDGEMENTS
The authors w u l d l i k e t o thank M r . E.J.A. van Dam, M r . J.F. van Lent and D r .
W.G. S l o o f o f t h e Laboratory o f M e t a l l u r g y f o r Electron-Probe Microanalysis,
SEM and X-ray d f f r a c t i o n analyses as w e l l as f o r discussions. M r . J. Padmos i s
thanked f o r the AAS analyses.
REFERENCES
1. W.O. Haag, R.M. Lago and P.B. Weisz, Faraday Discuss. Chem. SOC., 72
(1981) 317.
2. M.F.M: Post, J. van Amstel and H.W. Kouwenhoven, i n "Proceedings, 6 t h
I n t e r n a t i o n a l Z e o l i t e Conference" (D.H. Olson and A. B i s i o , Eds.), p. 517.
Butterworths, Guildford, 1983.
3. P. Voogd and H. van Bekkum, Appl. Catal. 59 (1990) 311.
4. D.B. Shah, D.T. Hayhurst, G. Evanina and C.J. Guo, AIChE J. 34 (1988) 1713.
5. M. Ghamami and L.B. Sand, Z e o l i t e s , 3 (1983) 155.
6. R.W. Grow and E.M. Flanigen, U.S. Patent 4,061,724, (1977).
7. C.A. Fyfe, J.H. O'Brien and H. S t r o b l , Nature 326 (1987) 281.
8. R.J. Argauer and G.R. Landolt, U.S. Patent 3,702,886, (1972).
9. K. Yamagishi, S. Namba and T. Yashima, J. Catal., 121 (1990) 47.
10. P. Voogd and H. van Bekkum, i n "Proceedings o f an I n t e r n a t i o n a l Symposium
on Z e o l i t e s as Catalysts, Sorbents and Detergent B u i l d e r s " , (H.G. Karge
and J. Weitkamp, Eds.), p. 519, E l s e v i e r , Amsterdam, 1989.
11. C.D. Chang, C.T.-W. Chu, J.N. Miale, R.F. Bridget- and R.B. C a l v e r t , J. Am.
Chem. SOC., 106 (1984) 8143.
12. C.N. S a t t e r f i e l d , J.R. Katzer and W.R. Vieth, Ind. Eng. Chem., Fundam., 10
(1971) 478.
13. R.M. Moore and J.R. Katzer, AIChE J., 18 (1972) 816.
14. C.N. S a t t e r f i e l d and J.R. Katzer, Adv. Chem. Ser., 102 (1971) 193.
15. C.N. S a t t e r f i e l d and C.S. Cheng, AIChE J., 18 (1972) 724.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 479
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
I n f o r m a t i o n a b o u t Inass t r a n s f e r p r o c e s s e s d u r i n g h e t e r o g e n e o u s
c a t a l y t i c r e a c t i o n s on m i c r o p o r o u s s o l i d s h a s become o f s p e c i a l
i m p o r t a n c e . To i n v e s t i g a t e b o t h s o r p t i o n a n d k i n e t i c s o f t r a n s p o r t
and r e a c t i o n o f e d u c t s and p r o d u c t s , e s p e c i a l l y o f t h e d i s p r o p o r -
t i o n a t i o n o f e t h y l b e n z e n e o n 13X z e o l i t e s , a h i g h p r e s s u r e a p p a -
r a t u s with a B e r t y r e c y c l e r e a c t o r i s described. D i f f u s i o n c o e f f i -
c i e n t s o f a r o m a t i c h y d r o c a r b o n s i n 13X t y p e z e o l i t e s a r e m e a s u r e d
as dependences o n t e m p e r a t u r e and c o n c e n t r a t i o n i n t h e n o n - r e a c -
t i o n s o r p t i o n r e g i o n b y means o f b o t h t h e h i g h - p r e s s u r e c h r o m a t o -
g r a p h i c t e c h n i q u e and t h e p i e z o m e t r i c method. I n p a r t i c u l a r , a
comparative study o f the transport parameters f o r the p - d i e t h y l -
b e n z e n e / l 3 X z e o l i t e s y s t e m i s c a r r i e d o u t . The d a t a o b t a i n e d a r e
i n g o o d a g r e e m e n t , e s p e c i a l l y i n t h e h i g h t e m p e r a t u r e r e g i o n . They
complement each o t h e r w i t h r e s p e c t t o t e m p e r a t u r e and c o n c e n t r a -
tion.
INTRODUCTION
I n t h i s work i t i s a t t e m p t e d t o d e t e r m i n e t h e c o e f f i c i e n t s o f
d i f f u s i o n a n d s o r p t i o n o f v a r i o u s a r o m a t i c h y d r o c a r b o n s o n 13X
t y p e z e o l i t e s b y means o f t h e h i g h p r e s s u r e c h r o m a t o g r a p h i c ( G C )
and t h e s o r p t i o n u p t a k e (SU) methods i n o r d e r t o a p p l y t h e r e s u l t s
t o t h e m o d e l l i n g and i n t e r p r e t a t i o n o f c o n t i n u o u s d i s p r o p o r t i o n a -
t i o n o f e t h y l b e n z e n e on a p p r o p r i a t e m o l e c u l a r s i e v e ( M S ) cata-
lysts. I n t h e GC (SU) s t u d y t h e t e m p e r a t u r e r a n g e i s 373 ...6 8 3 K
(373 ... 563 K ) a n d t h e p r e s s u r e r a n g e s f r o m v a l u e s less t h a n 1 T o r r
i n vacuo (SU) t o a b o u t 140 b a r ( G C ) . The t r a n s a l k y l a t i o n r e a c t i o n
w i l l b e p e r f o r m e d w i t h i n t h e same t e m p e r a t u r e r a n g e , b u t p r e s s u -
res t o b e u s e d w i l l b e h i g h e r t h a n 400 b a r i n o r d e r t o e x c e e d t h e
Besides the s o r p t i o n study, p r e l i m i n a r y explo-
c r i t i c a l point.
r a t i o n s a r e needed t o f i n d a most a c t i v e and s t a b l e c a t a l y s t f o r
the disproportionation reaction.
480
EXPERIMENTAL
The e x p e r i m e n t a l t e c h n i q u e s t o m e a s u r e m a s s f l u x e s o f s o r b i n g
s p e c i e s i n m i c r o p o r o u s c a t a l y s t s , e . g . MS c r y s t a l s , a r e c o n f r o n t e d
with t h e f o l l o w i n g problems:
- n o n - i s o t h e r m i c i t y of t h e s o r p t i o n p r o c e s s ;
- v e r y s m a l l p a r t i c l e (MS c r y s t a l ) s i z e s ;
- i n t e r p l a y between i n t r a c r y s t a l l i n e and i n t e r c r y s t a l l i n e t r a n s -
p o r t f o r p e l l e t s o r p a c k i n g s o f MS c r y s t a l s .
B e s i d e s t h e c l a s s i c a l SU m e t h o d , t h e G C e x p e r i m e n t s h a v e e v o l v e d
a s a major source f o r r e l i a b l e diffusionhon-equi1ibrium)data f o r
MS s y s t e m s . I n a d d i t i o n , t h e N M R t e c h n i q u e s h a v e e x t e n s i v e l y b e e n
u t i l i z e d t o determine s e l f - d i f f u s i o n c o e f f i c i e n t s (equilibrium
d a t a ) . U n f o r t u n a t e l y , one f r e q u e n t l y e n c o u n t e r s l a r g e d i s c r e p a n -
cies between v a r i o u s t y p e s of e x p e r i m e n t a l r a t e p a r a m e t e r s ,
e s p e c i a l l y f o r h i g h l y m o b i l e systems, e . g . f o r h y d r o c a r b o n s i n
13X t y p e z e o l i t e s . O f t e n t h i s f l a w i s b e i n g a t t r i b u t e d t o u n -
s a t i s f a c t o r y d e s i g n of experiments or improper measurement c o n d i -
t i o n s , c f . t h e reviews ( r e f s . 1-3). Therefore, i n t h i s investiga-
t i o n t h e i n f o r m a t i o n o n m o l e c u l a r t r a n s p o r t i s o b t a i n e d by t w o
i n d e p e n d e n t e x p e r i m e n t a l m e t h o d s , i . e . t h e GC a n d t h e SU
techniques.
Chromatographic method
I f o n e uses u n p e l l e t i z e d MS c r y s t a l s a s s o r b e n t , t h e d i s t r i b u -
t i o n o f c o n c e n t r a t i o n of a s o r b i n g m o l e c u l a r s p e c i e s b e t w e e n t h e
g a s e o u s a n d s o r p t i o n ( p a r t i c l e ) p h a s e s c a n b e d e s c r i b e d by t h e
following equations:
gaseous phase:
with
p a r t i c l e phase:
481
Fig. 1. Flow
diagram for
GC measure-
ments at high
pressures.
bl
chrornslopraphlc
column I
' U
-
- -- hsnlsd llnes
nmpllllsr recorder
F i g . 2. A r r h e n i u s p l o t s
f o r v a r i o u s systems
aromatic hydrocarbon/
NaX t y p e z e o l i t e
(values 0 obtained by
t h e GC t e c h n i q u e ; Do...
c o r r e c t e d by t h e
Darken eqn. benzene
( E / k J mol-1; 0 5 ) ; A t o -
lu8ne ( 6 9 ) ; O e t h y l b e n -
z e n e (72); a m - x y l e n e
(81).
-U
0)
ul
N
\
-5
Y
c
.-aJ
10-8
A
.-U
.c
Y -
g A
U
C
.-0
ul
3
Y-
'c
u ,040
1 2 3 I
concentration [ m o l e c u l e s / cage]
F i g . 3 . C o n c e n t r a t i o n dependence o f t h e d i f f u s i o n c o e f f i -
c i e n t o f p - d i e t h y l b e n z e n e o n NaX z e o l i t e a t 6 9 3 K ( o b -
t a i n e d by t h e GC t e c h n i q u e ) .
483
I-7-
--
- I
, t
t h e G C ( c r y s t a l s i z e 1...2 pm) a n d t h e p i e z o m e t r i c S U ( c r y s t a l
s i z e 8 0 pm) m e t h o d s . The r e s u l t s f r o m b o t h t e c h n i q u e s c o m p l e m e n t
e a c h o t h e r on t h e temoerature scale.
F i g . 5 . Compa-
r i s o n o f GC
( c i r c l e s ) and
SU ( s q u a r e s )
d i f f u s i o n data
f o r p-diethyl-
benzene on
NaX t y p e z e o l i -
tes.
S o r p t i o n method
I n t h e SU e x p e r i m e n t s a c o n s t a n t v o l u m e - v a r i a b l e p r e s s u r e
system w i t h v a l v e - e f f e c t c o r r e c t i o n s as d e s c r i b e d i n ( r e f s . 10,ll)
was e m p l o y e d . The v a l v e - e f f e c t c o r r e c t i o n s r e l a t e t o d e a d - t i m e
moments o f t h e a p p a r a t u s a m o u n t i n g t o s 0.2 s . To a v o i d t h e i n -
f l u e n c e o f i n t e r c r y s t a l l i n e d i f f u s i o n on t h e u p t a k e r a t e and t o
r e a l i z e quasi-isothermic conditions, SU was m e a s u r e d u s i n g ,
r e s p e c t i v e l y , a monolayer o f s i n g l e c r y s t a l s and f a v o u r a b l e e x t e r -
n a l temperature conditions ( i . e . , To< T v where t h e s u b s c r i p t s
o and v i n d i c a t e t h e dosed gas and z e o l i t e c r y s t a l phases, respec-
tively) (ref. 12). To e v a l u a t e d i f f u s i o n c o e f f i c i e n t s , the for-
m u l a s o f t h e s t a t i s t i c a l moments t h e o r y a s g i v e n p r e v i o u s l y ( r e f .
1 0 ) a r e u s e d . As i n t h e c a s e o f t h e GC d i f f u s i o n d a t a , the diffu-
s i o n c o e f f i c i e n t s t h u s d e r i v e d a r e t r e a t e d by t h e Darken e q u a t i o n
(ref. 3).
I n t h e p i e z o m e t r i c SU e x p e r i m e n t s t h r e e d i f f e r e n t l y s i z e d
samples o f l a b o r a t o r y - s y n t h e s i z e d 13X z e o l i t e a r e u s e d :
NaX ... 6 0 pm; 8 0 pm; NaKX ... 1 2 0 pm, 80% K+. The s i z e p a r a m e t e r s
given denote the diameter o f spheres c i r c u m s c r i b i n g t h e c r y s t a l s .
485
RESULTS
Fig. 6 shows concentration dependences of diffusion coefficients
for p-diethylbenzene on both NaX and NaKX in the temperature region
323 . . . 373 K. The following main results are evident:
- the diffusion coefficients coincide for both 13X specimens(with
different crystal sizes) except the data for lower loadings at
higher temperature, whereat the mobility o f p-diethylbenzene in
the NaX crystals seems to be lowered;
- the molecular mobility decreases strongly with increasing con-
centration in the intraccystalline void volume (this result
corresponds with the behaviour of other hydrocarbon/NaX type
systems (refs. 1 1 , 1 3 , 1 4 ) ) .
To provide further information on the behaviour of the p-diethyl-
benzene/NaX zeolite system at low concentration, a treatment of
corresponding SU rate curves by means of the computer programme
Z E U S (ref. 15) was carried out. An example is given in Fig. 7.
At least the conclusion can be drawn that with sufficiently low
concentration the molecular mobility of p-diethylbenzene in NaX
zeolite decreases most probably. This finding should be connected
with the comparatively strong interaction between aromatic molecu-
les and Na' cations. On the other hand, the decrease of diffusion
coefficients in the high concentration region can be explained by
increasing mutual interaction of molecules sorbed and by a reduced
free volume in the micropores (ref. 1 3 ) . As follows from Fig. 8
wherein a r e given the concentration dependences o f diffusion
coefficients of p-diethylbenzene on NaKX zeolite a t various tempe-
486
F i g . 6. Comparison o f
c o n c e n t r a t i o n dependen-
ces o f d i f f u s i o n c o e f f i -
c i e n t s o f p-diethylben-
z e n e o n NaX a n d NaKX
1 o.8 type zeolites a t various
temperatures
(SU experiments).
ro-'O
0.1 1.0
concentration [rnmol/g]
r a t u r e s up t o 5 6 3 K, t h i s e f f e c t becomes s u p p r e s s e d a t h i g h t e m p e -
r a t u r e s due t o i n c r e a s i n g k i n e t i c e n e r g y o f m o l e c u l e s s o r b e d i n
F i g . 7. S i -
mulation o f
a SU c u r v e
o f p-di-
ethylbenze-
n e o n NaX
zeolite at
3 7 3 K and
0.04 -1
mmol g
( + ) by t h e
software
ZEUS ( s o l i d
line).
487
03 1.o
concentration [mmol/g]
Fig. 9 . Arrhe-
nius plot of GC
(empty symbols)
and SU (full
symbols) data
for p-diethyl-
benzene on NaX
and NaKX type
zeolites, r e -
spect ively.
E, N 40 ItJ/rnol
at n N 0.8 rnrnol/g
10-'O F
more complex molecular structure of p-diethylbenzene.
If one takes into account that the GC measurements were carried
out in a temperature region where the diffusion coefficients r e -
main practically constant over a wide concentration region and,
on the other hand, this result is also confirmed by the SU measu-
rements, a good agreement can be stated for the data from both
methods. The SU method complements the GC technique at low tempe-
rature contributing information about an increasing influence of
concentration on intracrystalline molecular mobility. The low dif-
fusion coefficients of p-diethylbenzene at very low micropore
fillings of the NaX zeolite - as shown by the GC technique - is
suggested by the SU results as well.
The molecular mobility data described will serve as reliable
information on intracrystalline transport for further considera-
tion of reaction kinetics.
CONCLUSIONS
The principle of an experimental high pressure chromatographic
system with a Berty recycle reactor to study sorption,diffusion
and reaction on columns with crystals of molecular sieves is
described.
489
ACKNOWLEOGEMENTS
W.H. and G . E . thank the Oeutsche Forschungsgemeinschaft for
financial support. M.B. thanks the Akademie der Wissenschaften der
D D R for the possibility to work on diffusion phenomena in molecu-
lar sieve systems.
NOTATIONS
D diffusion coefficient
?3x
coefficient of axial dispersion
K constant of sorption equilibrium
L column length cm
mass flux density across the m m o l cm
-2 s -1
NRc zeolite crystal interface (cf.eqn.2)
RC
external r a d i u s of zeolite crystals cm
C gaseous phase concentration mmol cm-3
9
CT total sorbate concentration in mmol cm-3
gaseous phase
C
* = Kc , sorbate concentration in mmol cm-3
intrgcrystalline void volume o f
zeolite
r radial coordinate of zeolite crystal cm
t time S
490
-1
V l i n e a r gas v e l o c i t y cm s
X molar f r a c t i o n -
' i n t e r p a r t i c l e v o i d volume of
column p a c k i n g (volume f r a c t i o n )
-
REFERENCES
1 J . K a r g e r a n d D.M. R u t h v e n , Z e o l i t e s , 9 ( 1 9 8 9 ) 2 6 7 - 2 8 1 .
2 H.W. H a y n e s , J r . , C a t a l . Rev. - S c i . E n g . , 30 ( 1 9 8 8 ) 5 6 3 - 6 2 7 .
3 M. B u l o w , J . K a r g e r , M . K o z i r f k a n d A . M . V o l o g z u k , Z . Chem.,
L e i p z i g , 2 1 (1981) 175-182.
4 D.M. Ruthven and M. E i c , Z e o l i t e s , 8 (1988) 40-45.
5 A . S . C h i a n g , A . G . D i x o n a n d Y . M . Ma, Chem. Eng. S c i . , 3 9 (1984)
1451-1459.
6 W.J. Thomas a n d U . U l l a h , Chem. Eng. Res. D e v . , 6 6 ( 1 9 8 8 ) 138-
146.
7 N . A . C o l l i n s , P . G . O e b e n e d e t t i a n d 5. S u n d a r e s a n , A I C h E J . , 3 4
(1988) 1211-1214.
8 G . Manos, Ph. 0 . T h e s i s " U n t e r s u c h u n g e n d e r V e r k o k u n g v o n
Z e o l i t h e n und i h r e r R e a k t i v i e r u n g m i t u b e r k r i t i s c h e n F l u i d e n "
U n i v e r s i t a t E r l a n g e n - Nurnberg, 1989.
9 H . S c h a f e r , Ph. 0 . T h e s i s " U n t e r s u c h u n g e n z u r K i n e t i k d e r Des-
a k t i v i e r u n g und R e a k t i v i e r u n g p o r o s e r K o n t a k t e m i t u n t e r - bzw.
u b e r k r i t i s c h e n R e a k t i o n s g e m i s c h e n " U n i v e r s i t a t E r l a n g e n - Nurn-
b e r g , 1990.
10 P . S t r u v e , M . KoEi??<k, M. Bulow, A . Z i k a n o v a a n d A . G . B e z u s ,
Z . p h y s . Chem., L e i p z i g , 264 ( 1 9 8 3 ) 4 9 - 6 0 .
11 M. Bulow, P. L o r e n z , W. M i e t k , P . S t r u v e and N.N. S a m u l e v i x ,
J . Chem. S O C . , F a r a d a y T r a n s . I , 7 9 ( 1 9 8 3 ) 1 0 9 9 - 1 1 0 8 .
12 M. B u l o w , P . S t r u v e a n d W . M i e t k , Z . p h y s . Chem., L e i p z i g ,
267 ( 1 9 8 6 ) 6 1 3 - 6 1 6 .
13 J . K a r g e r , H. P f e i f e r , M. R a u s c h e r a n d A . W a l t e r , J . Chem. S O C . ,
Faraday Trans. I , 7 6 (1980) 717-729.
14 M . B u l o w , W . M i e t k , P . S t r u v e a n d P . L o r e n z , J . Chem. S o c . , F a r a -
day T r a n s . I,79 ( 1 9 8 3 ) 2 4 5 7 - 2 4 6 6 .
15 M . B u l o w a n d A . M i c k e , K a t a l y s e , D e c h e m a - M o n o g r a p h i e Ed. 1 1 8 ,
VCH V e r l a g s a n s t a l t , F r a n k f u r t / M . , 1989, p. 349-355.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 491
0 1991 Elsevier Science Publishers B.V., Amsterdam
ABSTRACT
I n t h e p r e s e n t s t u d y i t has been shown t h a t t h e propene igomerization a c t i v i t y
o f ZSM-5 a t 5MPa and 220-290°C i s m a i n l y dependent on t h e aluminium c o n t e n t and
c r y s t a l s i z e o f t h e c a t a l y s t . Optimum a c t i v i t i e s and l i f e t i m e s were o b t a i n e d
w i t h Si/A1 = 40, c r y s t a l s i z e < lpm and a s y n t h e s i s t i m e o f 3 days. T his
y i e l d e d under optimum r e a c t i o n c o n d i t i o n s a c a t a l y s t u t i l i z a t i o n v a l u e o f 1100
g.liq/g.cat. E x t r u d i n g t h e c a t a l y s t u s i n g alumina as a b i n d e r d i d n o t a d v e r s e l y
affect the activity, selectivity or lifetime o f the catalyst. Pelletizing
reduced t h e a c t i v i t y o f t h e c a t a l y s t . A m e c h a n i c a l l y - s t i r r e d autoclave l e d
t o a decrease i n t h e t h e average c r y s t a l s i z e and a narrower s i z e d i s t r i b u t i o n .
A number o f t e mp l a t e s were used i n t h e s y n t h e s i s o f ZSM-5 and 1,6-hexanediamine
and 1,2-cyclohexanediamine produced c a t a l y s t s w i t h s i m i l a r c a t a l y t i c p r o p e r t i e s
t o t h o s e prepared u s i n g tetrapropylammonium bromide.
INTRODUCTION
ZSM-5 has been shown t o be an e x c e l l e n t c a t a l y s t f o r t h e c o n v e r s i o n o f
l i g h t o l e f i n s t o l i q u i d f u e l s ( r e f s . 1 - 4 ) . I n general t h e a c t i v i t y i s r e l a t e d t o
t h e A1 c o n t e n t ( r e f s . 5-7). The c r y s t a l s i z e a l s o increases as Si/A1 ratio
inc re as es ( r e f . 8 ) . The a c t i v i t y o f v a r i o u s c a t a l y t i c r e a c t i o n s i n c r e a s e s as
c r y s t a l s i z e decreases ( r e f s . 9-10). The need t o f orm e x t r u d a t e s and p e l l e t s
fro m t h e powder can a l s o s t r o n g l y i n f l u e n c e t h e s e l e c t i v i t y and a c t i v i t y o f t h e
c a t a l y s t ( r e f s . 11-14). Longer c r y s t a l 1 i z a t i o n t imes enhance t h e c o n c e n t r a t i o n
o f A1 on t h e e x t e r n a l s u r f a c e sometimes r e s u l t i n g i n a s h o r t e r c a t a l y s t l i f e
( r e f . 15). The use o f a l t e r n a t i v e templates i n t h e s y n t h e s i s o f ZSM-5 has a l s o
been e x t e n s i v e l y s t u d i e d ( r e f s . 16-20).
T h i s paper p r e s e n t s r e s u l t s o b t a i n e d i n a s t u d y o f t h e e f f e c t o f S i / A l
r a t i o , s y n t h e s i s t i m e , t e m p l a t e s and s t i r r i n g mechanism on t h e c h a r a c t e r i s t i c s
o f ZSM-5 and on i t s a c t i v i t y , s e l e c t i v i t y and l i f e t i m e f o r t h e o l i g o m e r i z a t i o n
o f propene i n a h i g h p r e s s u r e f i x e d bed r e a c t o r . Powdered c a t a l y s t samples were
a l s o e x t ruded and p e l l e t i z e d u s i n g v a r i o u s b i n d e r s and t h e e f f e c t s o f t h i s
t r e a t m e n t on l i f e t i m e and s e l e c t i v i t y was s t u d ied.
EXPERIMENTAL
Samples o f ZSM-5 were s y n t h e s i z e d a c cording t h e method o f Argauer and
L a n d o l t ( r e f . 21) u s i n g b o t h m e c h a n i c a l l y and m a g n e t i c a l l y s t i r r e d a u t o c l a v e s .
492
D e t a i l s o f the method are given elsewhere ( r e f s . 22,23). The samples used are
r e f e r r e d t o as (A)-Z-X-Y where A = template (tetrapropylammonium bromide unless
otherwise stated), Z = ZSM-5, X = S i / A l r a t i o and Y = synthesis time. Three
types of templates were used, viz. tetra-alkylammonium ions, amines and
alcohols. The f i r s t category included methyl (TMA), e t h y l (TEA), propyl (TPA)
and b u t y l (TBA) ammonium bromide. The amines used were 1,2 ethanediamine (1,2
ED), 1,2 propenediamine (1,2 PD), 1 butylamine (1 BA), 1 hexylamine (1 HA), 1,6
hexanediamine (1,6 HD) and 1,2 cyclohexanediamine (1,2 CHD). A number o f
alcohols were a l s o used. The c a t a l y s t s were characterized using SEM, EDX, XRD,
ammonia TPD and, i n some cases, MASNMR.
TABLE 1
18 1 1.8
44 1 0.8
64 1 1.1
131 1 1.4
197 1 1.8
487 1 4.7
48 3 1.1
43 6 1.2
45 10 1.2
19 3 2.9
26 6 3.0
493
TABLE 2
E f f e c t o f s t i r r i n g on average c r y s t a l Size
(Synthesis time = 3 days)
100
C
0
n
V
e 80
r
0
I
0
n 80
0
I
40
P
r
0
P
n
e
x 0'
0 2 4 6 8 10 12 14 16 18
Time on stream (hrs)
Fig. 2 E f f e c t o f c r y s t a l s i z e on c a t a l y s t u t i l i z a t i o n value.
495
385 g/g and t h e i r magnetically s t i r r e d equivalents were 286 and 258 g/g
r e s p e c t i v e l y . Their c r y s t a l sizes are shown i n Table 2.
2 Ton9
5 Tons
0 5 10 15 20 25 30 35 40 45
Time on stream (hr)
40
Mass%
30
20
10
0
Dlmer Trimer Tetramer Pentamer Hexamer,
Oligomer Group
Powder @ Silica extrudates 0Alumina Extrudetes
Fig. 4 Liquid Product Analysis
497
DISCUSSI ON
The number average crystal sizes of 2-18-1, 2-19-3 and 2-26-6 were larger
than what was expected from the trend observed by Van der Gaag et a1 .(ref. 25)
and Jacobs and Martens (ref. 13). For the 6-day catalyst this may be due to
amorphous material being deposited on the zeolite surface. The increase in
crystal size (2-19-3 and 2-26-6 larger than 2-18-1) has been observed by other
workers (ref. 26). Mechanical stirring is expected to cause more attrition than
a magnetic stirrer bar in a synthesis mixture and hence as observed in the
present study should cause a decrease in crystal size. The narrow size
distributions obtained with mechanical stirring could be a result of more
effective agitation throughout the autoclave and a more even distribution of
stress on the crystals. This is distinctly advantageous with respect to the
propene oligomerization activity. When different templates were used it was
found that 1 BA, 1,2 ED, 1,2 PD as well as the alcohol-based samples produced
larger crystal sizes than TPA-ZSM-5. This may happen if the formation of the
template-silicate complex is difficult resulting in the formation of only a few
nuclei which then grow to a larger size.
The synthesis used in this study was similar to type ‘A’ of Gabelica et
al. (ref. 27), who reported an aluminium rich outer layer for this synthesis
procedure. Aluminium zoning of this nature was reported by Von Ballmoos and
Meier (ref. 28). Suzuki et al. (ref. 29) also confirmed this finding and
observed a decrease in activity for methanol conversion as synthesis time
increased once maximum crystal1 inity was attained. They attributed the decrease
in activity to increased coking on the catalyst surface. The results of the
present study support these observati ons.
This work has shown that a decrease in crystal size enhances lifetime and
activity for propene ol igomerization as has been reported for methanol
498
conversion (ref. 3 0 ) , xylene isomerisation (ref. 31) and propene oligomer sation
using N i - and Zn-impregnated ZSM-5 (ref. 3 2 ) .
The low crystallinities and primarily the large crystal sizes of the
alcohol-based ZSM-5 samples were probably responsible for their low activities
and short lifetimes. Surprisingly extrusion did not decrease the activity for
propene ol igomerization although the high conversions involved may have masked
any difference in activity between powdered and extruded catalysts. Attempts to
verify this observation at low conversions were difficult due to temperature
runaway problems. The observed decrease in lifetime and activity with
increasing pelletisation pressure is probably due to increased diffusional
resistance in the intercrystalline pores and blockage of the ZSM-5 micropores by
binder particles.
CONCLUSION
T h i s s t udy has shown t h a t a t Si/A1 r a t i o s o f about 40, t h e c r y s t a l s i z e o f
ZSM-5 has a c r i t i c a l e f f e c t on propene o l i g o m e r i z a t i o n a c t i v i t y . S m a l l e r s i z e
and narrow er c r y s t a l s i z e d i s t r i b u t i o n s a r e o b t a i n e d when u s i n g m e c h a n i c a l l y
s t i r r e d a ut o c lav e s . When t h e powder i s e x t r uded t h e r e i s no adverse e f f e c t on
o l i g o m e r i z a t i o n a c t i v i t y and when alumina i s used as a b i n d e r b e t t e r q u a l i t y
distillate fuel i s produced. P e l l e t i z i n g t h e powder reduces a c t i v i t y in
p r o p o r t i o n t o t h e p r e s s u r e s used. Other t e m plat es such as 1,6 hexanediamine and
1,2 cyclohexanediamine produce ZSM-5 o f s i m i l a r a c t i v i t y t o TPA-based ZSM-5 b u t
o t h e r amines and a l l a l c o h o l s t e s t e d produced poor o l i g o m e r i z a t i o n c a t a l y s t s .
ACKNOWLEDGEMENT
The a ut h or s w i s h t o acknowledge f i n a n c i a l support f r o m t h e U n i v e r s i t y o f
Cape Town, N a t i o n a l Energy Council and Sasol .
REFERENCES
1 S.A. Tabak, F.J. Krambeck and W.E. Garwood, J.AIChE, 32(9) (1986) 1529.
2 R.J. Ouann. L.A. Green, S.A. Tabak and F.J. Krambeck, I n d . Eng. Chem.
Res., '27 (1'988) 567. .
3 M.L. O c c e l l i , J.T. Hsu and L.G. Galya, J. Mol. Cat al. , 32 (1985) 378.
4 K.G. W i l s h i e r , P. Smart, R. Western, T. Mole and T. Behrsing, Appl.
C at a l. . 31 119871 345.
5 S. B e s s e l l and 0: Seddon, J. Catal., 105 (1987) 272.
6 S.P. Zhdanov, N.N. Fe o k t i s t o v a , N . I . Kozlova, N.R. Bursian, S.B. Kogan,
V.K. Daragan and N.V. Aleksandrova, Acta Phys. Chem., 31 (1985) 131.
7 V.S. Nayak and V.R. Choudary, Appl. C a t al. , 4 (1982) 339.
8 F.J. van d e r Gaag, J.C. Jansen and H. van Bekkum, Appl. C a t a l . , 17 (1985)
264.
9 M. Sugimoto, H. Katsuno, K. Takatsu and N. Kawata, Z e o l i t e s , 7 (1987) 503.
10 P. Ratnasamy, G.P. Babu, A.J. Chandwadkar and S.B. K u l a r n i , Z e o l i t e s , 6
(1986) 98.
11 M.L. O c c e l l i , J.T. Hsu and L.G. Galya, J . Molec. Cat al. , 32 (1985) 379.
12 U. Hammon, M. K o t t e r and L. R i e k e r t , Appl. Cat al. , 37 (1988) 155.
13 P.A. Jacobs and J.A. Martens, S t u d i e s i n Surf ace Science and C a t a l y s i s , 33
(1987) 72.
500
SUMMARY
Systematic studies of the SAPO-5 system have been performed. Roth the
crystal size and shape as well as the phase purity can be controlled by the
reacting gel composition and also by the duration and/or temperature of crys-
tallization. Evidence is given for the interdependence between the shape of
crystals and their sorption properties.
INTRODUCTION
Porous silicoaluminophosphates (ref. 1) are promising materials for numer-
ous scientific and potential practical applications. However, thoroughly re-
fined applications require materials of strictly defined physical featiires,
e.g. crystal size and shape. Unfortunately, the control of these parameters in
the case of zeolitic materials did not represent a field of major interest un-
til now, except for the tailoring of type A zeolites for washing powder produc-
tion (refs. 2 , 3 cited in ref. 4) and for the growing of MFI type crystals
(refs. 5-10). Obviously, the growth of tailored crystals requires the knowledge
of both the kinetics of the process and the conditions enabling the formation
of larger crystals. The latter problem has been solved for both the AlPO4-5
(refs. 11-16) and the SAPO-5 molecular sieves ( r e f s . 17-19). Recently, the
kinetics of SAPO-5 crystallization has been investigated in detail (ref. 2 0 )
but not with respect t o the size of the crystals.
We aim at a better understanding of the SAPO-5 crystallization process and
at getting control of size and shape of the crystals. The paper presents a num-
ber of results and conclusions regarding these goals.
EXPERIMENTAL
SAPO-5 molecular sieve crystals were synthesized hydrothennally in teflon-
lined steel autoclaves in air-heated w e n s at 4 5 3 to 473 K from gels of the
formal molar composition
a A1203 * b P2O5 - c TEA d Si02 e H20 * x H2SO4 (1)
with a = 1, b = 1 t o 2.4, c = 1.5 t o 12, d = 0.05 t o 1 , e = 300 t o 2000, x ? 0.
F i r s t , g e l s were formed by mising a s t a b i l i z e d aluminiumoxidehydrate
s o l ( p u r c h a s e d from CTA SAURESCHUTZ, B e r l i n ) w i t h s i l i c a s o l (LUDOX AS 40 from
DUPONT/Germany). Next, a s o l u t j o n of 85% p h o s p h o r i c a c i d and t r i e t h y l a m i n e / T E A /
(Merck) i n t w i c e d i s t i l l e d w a t e r was added under v i g o r o u s s t i r r i n g . Varioiis
amounts o f H3PO4, TEA, and w a t e r were admixed a c c o r d i n g t o t h e g e l rompr~siticln
s t u d i e d . A t t h e same t i m e , s u l f u r i c a c i d was added, i f n e c e s s a r y , t o a d j u s t t h e
pH v a l u e t o 3 , 3 + 0 , 2 . A s e r i e s of r u n s was made a t d = 0 t o grow AlP04-5 c r y s -
t a l s a s r e f e r e n c e samples.
These g e l s were p u t i n t o t h e a u t o c l a v e s and exposed t o t h e c r y s t a l l i z a t i o n
t e m p e r a t u r e . A f t e r a p p r o p r i a t e time p e r i o d s , t h e v e s s e l s were c o o l e d down, t h e
samples were washed, s e p a r a t e d from b y p r o d u c t s , i f n e c e s s a r y , by d e c a n t a t i o n
( o b v i o u s l y , a number of smaller SAPO-5 c r y s t a l s were l o s t a t t h e same t j m e ) ,
and d r i e d a t 3 7 3 K. Furthermore, s e l e c t e d samples were c a l c i n e d under s t a t i c
a i r atmosphere a t about 1050 K f o r 24 h r s .
The p r o d u c t s were c h a r a c t e r i z e d by XRD ( G u i n i e r t e c h n i q u e ) , MAS NMR, I R
s p e c t r o s c o p y , a d s o r p t i o n , and SEM. The c o n t e n t of c r y s t a l s i n t h e samples was
e s t i m a t e d and t h e c r y s t a l dimensions were measured by l i g h t microscopy accor-d-
i n s t o t h e methods d e s c r i b e d i n d e t a i l e l s e w h e r e ( r e f . 2 1 ) .
RESUILTS
The procedure e l a b o r a t e d ( r e f s . 17-19) i s a r e l i a b l e r c c j p e € o r t h e syn-
t h e s i s of l a r g e hexagonal SAPO-5 p r i s m s , though sometimes i n a broad p a r t i c l e
s i z e d i s t - r i b u t i o n . I n comparison w i t h t h e similar p r o c e d u r e t o grow A1P04-5
m o l e c u l a r s i e v e s ( r e f s . 13-16), t h e SAPO-5 s y s t e m is more complex. However, t h e
c r y s t a l s o b t a i n e d i n a l l e x p e r i m e n t s e x h i b i t X-ray p a t t e r n s c o r r e s p o n d j n g t o
t h e A F I topology and MAS NMR measurements prove s i l i c o n i n c o r p o r a t i o n i n t o t h e
framework.
The c r y s t a l l i z a t i o n was s t u d i e d w i t h i n t h e range of t e m p e r a t u r e from 423
t o 4 7 3 K and p e r i o d s up t o 10 days. Whereas a t t h e lower l i m i t of t.emperature
f o r e i g n phases a r e formed, t h e c r y s t a l l i z a t i o n of SAPO-5 is a c c e l e r a t e d w i t h
r i s i n g t e m p e r a t u r e . T h i s l e a d s t o y i e l d s of SAPO-5 up t o 100 p e r c e n t depending
on t h e g e l composit.ion. A t 463 K , t h e l a r g e s t c r y s t a l s were obt.ained. There-
f o r e , we r e p o r t o n l y about t h e e x p e r i m e n t s a t t h i s t e m p e r a t u r e ,
The g e l c o m p o s i t i o n r e p r e s e n t s t h e most i m p o r t a n t f a c t o r f o r t h e c o n t r o l
of b o t h c r y s t a l s i z e and s h a p e . To t h e d e g r e e t o which t h e r o l e of s j l i c o n can
be n e g l e c t e d , i . e . a t s u f f i c i e n t l y low s i l i c a c o n c e n t r a t i o n i n t h e gel, t h e
e f f e c t s of c o n t e n t s of H 2 0 , TEA, and P2O5 are s i m i l a r t o t h o s e which govern t h e
n u c l e a t i o n and growth of AlPO-5 c r y s t a l s ( r e f . 1 6 ) . The i n f l u e n c e s of b o t h t h e
c o n t e n t of H 2 0 ( F i g . 1 ) and t h e c o n t e n t of TEA o r TEA and P2O5 t o g e t h e r ( F i g . 2 )
503
Fig. 1. SAPO-5 crystals (after decantation) synthesized from gels with rising
water content (a:b:c:d = 1:1:1.55:0.2):
( A ) e = 300, (B) e = 450, ( C ) e= 600, (D) e = 750.
504
Fig. 2. SAPO-5 crystals (after decantation) synthesized from gels with constant
water content (e = 300 H20, d = 0 . 2 Si02):
( A ) b = 1 , c = 1.55; ( B ) b = I , c = 3.1,; ( C ) b = 1, c = 6 . 2 ; (D) b = 2, c =
3.1.
6 00- I
/
0 1.55 0.2 +,
1 3.1 0.2
E 400- 1 6.2 0.2
-2
E
-.
-
2 3.1 0.2 0
200-
I I
I I I I I
400 600 800 H20ImoLe
Fig. 3. Maximum length of AFI hexagonal prisms depending on the gel
composition.
505
1 I I I 1 I I I
-2 .4 .6 .8 PIP,
CONCLUSIONS
The s t u d i e s performed have shown t h e c o n d i t i o n s € o r t a i l o r i n g t h e c r y s t a l s
of t h e SAPO-5 molecular s i e v e w i t h c r y s t a l s i z e s r a n g i n g from 25 t o 580 pm i n
508
l e n g t h . P a r t i c u l a r a t t e n t i o n h a s been p a i d t o t h e c o n d i t i o n s i n f l u e n c i n g c r y s -
t a l morphology.
The f o r m a t i o n and growth of t h e c r y s t a l s a r e i n f l u e n c e d by t h e c o n t e n t of
a l l components i n t h e g e l . D i l u t i o n of t h e s y s t e m enhances t h e growth a l o n g t h e
c-axis l e a d i n g t o t h e f o r m a t i o n of l a r g e hexagonal p r i s m s . On t h e o t h e r h a n d ,
an e x c e s s of amine o r amine and p h o s p h o r i c a c i d t o g e t h e r r e s t r i c t s t h e c r y s t a l
growth v i a an a c c e l e r a t i o n of t h e n u c l e a t i o n r a t e . Then, t h e d i s t o i . t e d c r y s t a l s
o r even growth a g g r e g a t e s a r e formed.
The s i l i c o n c o n t e n t r e p r e s e n t s a n a d d i t i o n a l v a r i a b l e i n f l u e n c i n g t h e
c r y s t a l shape. The e u h e d r a l hexagonal p r i s m s c a n c r y s t r a l l i z e o n l y from g e l s
c o n t a i n i n g up t n about 0 . 3 s i l i c o n ( m o l a r r a t i o ) which is incorporat.ed i n t o t h e
s t r u c t u r e a l m o s t o n l y on phosphorus-T-sites.
The f o r m a t i o n of t h e p u r e SAPO-5 phase is c o r r e l a t e d w i t h t h e c o n d i t i o n
H?O/TEA < I 0 0 ( m o l a r r a t i o ) . T h e r e f o r e , l a r g e hexagonal SAPO-5 prisms a r e always
accompanied by s m a l l p a r t i c l e s of an u n i d e n t i f i e d aluminophosphate which can be
s e p a r a t e d , i n p r i n c i p l e , because of t h e l a r g e d i f f e r e n c e s i n t h e s i z e of t.he
particles.
The shape of t h e c r y s t a l s i n f l u e n c e s c o n s i d e r a b l y t h e i r s o r p t i o n
properties.
ACKNOWLEDGEMENTS
The authoi i a r e i n d e b t e d t o Dr. Janchen f o r a d s o r p t i o n measurements and t o
D I . M . Hndnn f o r h e l p f u l d i s c u s s i o n s . Thr work was p a r t i a l l y s u p p o r t e d by Leuna
WilrkF' AG. by t h e fund of t h e P r e s i d e n t of t h e Academy of S c i e n c e s of tht, GDR,
and by t h e P o l i s h M i n i s t r y of N a t i o n a l Education w i t h i n t h e P r o j e c t CPBP 01.06.
REFERENCES
1 B.M. I n k . C . A . Messina, R . L . P a t t o n , R.T. Gajek, T.R. Cannan, and E.M.
Flanigeri, I . Am. Chem. SOC., 106 ( 1 9 8 4 ) . 6092.
2 DE 2 517 218 ( 1 9 8 6 ) .
3 I)F 2 660 726 ( 1 9 8 6 ) .
4 W. Leonhardt and 9.-M. Sax, Stud. S u r f . S c i . Catal., 46 ( 1 9 8 9 ) , 691.
5 R. Mostowicz and J . M . Berak, Proc. I n t . Symp.: " Z e o l 7 t e s - S y n t h e s i s ,
S t r u c t u r e , Technology, and A p p l i c a t i o n " , P o r t o r o s e , 1984, B. DrZaJ, S .
Hocevar, and S . Pejovnik ( E d s . ) , E l s e v i e r , Amsterdam, 1985, pp. 65-72.
6 E.G. Derouane and 2. G a b e l i c a , J . S o l i d S t a t e Chem., 64 (19861, 296.
I S . F r n s t , P.A. J a c o b s , J . A . Martens, and J. Weitkamp, Z e o l i t e s , L ( 1 9 8 7 ) .
458.
8 J . Kornatowski, Z e o l i t e s , 7 ( 1 9 8 7 ) . 7 7 .
Y D.T. Hayhurst, A. N a s t r o , E. A i e l l o , F. C r e a , and G . Giordano, Z e o l i t e s ,
(19881, 416.
10 F . Crea, A . N a s t r o , .J.B. Nagy, and R. A i e l l o , Z e o l i t e s , S ( 1 9 8 8 ) , 262.
11 U . M u l l e r , A. Brenner, A . Reich, and K . K . Unger, ACS Symp. S e r . , 398
( 1 9 8 5 ) , 347.
12 S . Qiu, W . Pang, H . K e s s l e r , and J.-L. Guth, Z e o l i t e s , 2 ( 1 9 8 9 ) . 440.
13 G. F i n g e r , J. Kornatowski, M. Bulow, and M. Rozwadowski, DD WP 330 56512
(1985).
509
' C e n t r a l I n s t i t u t e o f P h y s i c a l C h e m i s t r y , Academy o f S c i e n c e s ,
Rudower Chaussee 5, B e r l i n - 1 1 9 9 (GDR)
2Department o f C h e m i s t r y , K a r l - M a r x - U n i v e r s i t y Leipzig,
T a l s t r a R e 35, L e i p z i g - 7 0 1 0 (GDR)
SUMMARY
O n t h e b a s i s o f s y s t e m a t i c a l l y d e v e l o p e d s u b u n i t c l u s t e r mod-
e l s o f NaX z e o l i t e framework n o r m a l c o o r d i n a t e a n a l y s e s h a v e
been c a r r i e d o u t by means o f WILSON'S GF m a t r i x method i n t e n d i n g
t o u n d e r s t a n d t h e c o r r e s p o n d i n g e x p e r i m e n t a l v i b r a t i o n a l spec-
t r a . An a p p r o x i m a t e a s s i g n m e n t o f v i b r a t i o n a l f r e q u e n c i e s o f t h e
NaX z e o l i t e framework i s g i v e n o n t h e b a s i s o f c a l c u l a t e d e i g e n -
v a l u e s , p o t e n t i a l e n e r g y d i s t r i b u t i o n s and e i g e n v e c t o r s . The r e -
s u l t s a r e d i s c u s s e d i n c o n n e c t i o n w i t h t h e FLANIGEN c o n c e p t i o n
o f i n t e r n a l and e x t e r n a l v i b r a t i o n s .
INTRODUCTION
Z e o l i t e s have been w i d e l y used f o r i o n exchange, s e l e c t i v e
a d s o r p t i o n and c a t a l y s i s . Related t o t h a t r e s u l t s o f a great
number o f e m p i r i c a l s t u d i e s o f i n f r a r e d and Raman s p e c t r a have
been p u b l i s h e d m a i n l y c o n c e r n i n g w i t h OH s t r e t c h i n g v i b r a t i o n s
and more r e c e n t l y c o n s i d e r i n g t h e v i b r a t i o n s o f t h e z e o l i t e
framework on t h e b a s i s o f FLANIGEN c o n c e p t i o n ( r e f . 1). I n t h e
most c a s e s t h e r e a r e d i f f i c u l t i e s w i t h r e s p e c t t o t h e i n t e r p r e -
t a t i o n o f v i b r a t i o n a l s p e c t r a because o f t h e c o m p l i c a t e d c r y s t a l
s t r u c t u r e on one s i d e and t h e s t r o n g l y o v e r l a p p e d bands i n t h e
z e o l i t e s p e c t r a on t h e o t h e r s i d e . Beside t h a t i t i s i n s u f f i -
c i e n t l y known t h e i n f l u e n c e o f c a t i o n s , s t r u c t u r a l OH g r o u p s ,
a d s o r b e d w a t e r and o t h e r m o l e c u l e s on t h e v i b r a t i o n a l spectrum.
F u r t h e r d i f f i c u l t i e s a r i s e w i t h i n a more t h e o r e t i c a l t r e a t -
ment o f v i b r a t i o n a l b e h a v i o u r o f z e o l i t e s c o n n e c t i n g w i t h t h e
l a r g e u n i t c e l l s and t h e i n s u f f i c i e n t l y known f o r c e r e l a t i o n s
between t h e l a t t i c e atoms and i o n s . The n o r m a l c o o r d i n a t e a n a l y -
s i s a s a r o u t i n e method c a n be u s e d t o i n t e r p r e t v i b r a t i o n a l
spectra, but i s r e s t r i c t e d t o the s o l u t i o n o f d i r e c t eigenvalue
p r o b l e m s because o f t h e l a c k o f e x p e r i m e n t a l d a t a f i t t i n g t h e
model f o r c e c o n s t a n t s . So f a r some n o r m a l c o o r d i n a t e a n a l y s e s
512
TABLE 1
D i s t r i b u t i o n o f n o r m a l v i b r a t i o n s o n t h e symmetry s p e c i e s o f
d i f f e r e n t z e o l i t e c l u s t e r models
S i 0 4 , A104 9 9
O3 S i -0 ( i) -A103 21 21
4R(hP), 4R(S)- 42 42
6 R ( h P ) ; /C3/ r=22a+22e 44 44
06R; /S6/ r=20au t 2oa + 20eu+20e 40 40
9 9
Si04(A1)4 r=21a 21 21
Si04 (A103)4 r=57a 57 57
A104 P i 0 3 14 ( A 1 19 r=84a 84 84
A124Si24096 ; /Fd3, (Th 4 ) / r=18A +18Au+18E +18Eu+ 53
90
9 9
54 Fa+53F,
600 400
l o w e r f r e q u e n c i e s by s t r o n g c o u p l i n g s . T h i s r e s u l t i s supported
by FLANIGEN's i n f r a r e d s t u d i e s o f sodium a l u m o s i l i c a t e s i n d i f -
ferent crystallization states (ref. 16). Increasing the crystal-
l i z a t i o n degree and t h u s d e c r e a s i n g t h e number o f t e r m i n a l bonds
i n t h e m i x t u r e l e a d s t o d i s a p p e a r a n c e o f an a b s o r p t i o n band a t
850 cm" c h a r a c t e r i z i n g t e r m i n a l A 1 0 bonds.
The c a l c u l a t e d f r e q u e n c y r e g i o n s o f s t r e t c h i n g and OTO bend-
ing vibrations, t o g e t h e r w i t h an a p p r o x i m a t e c l a s s i f i c a t i o n o f
t h e model v i b r a t i o n s a r e c o l l e c t e d i n t h e T a b l e s 2 and 3. The
TOT b e n d i n g s and t o r s i o n a l v i b r a t i o n s a p p e a r i n g i n t h e f a r i n -
f r a r e d r e g i o n a r e n o t s u b j e c t o f t h i s s t u d y . V i b r a t i o n a l modes
o f t h e s u b u n i t c l u s t e r models d e t e r m i n e d by t h e p o t e n t i a l e n e r g y
d i s t r i b u t i o n and t h e e i g e n v e c t o r s show a c o m p l i c a t e d p i c t u r e .
I t c a n be d i s t i n g u i s h e d between 3 t y p e s o f s t r e t c h i n g v i b r a -
tions: terminal, bridging ( w i t h regard t o linkages connecting 2
t e t r a h e d r o n s ) and t e t r a h e d r a l v i b r e t i o n s , a l l o f t h e s e c a n be
f u r t h e r d i v i d e d i n s y m m e t r i c and a s y m m e t r i c ones. I n addition t o
t h i s t h e p o t e n t i a l e n e r g y can be d i s t r i b u t e d i n a d i f f e r e n t way.
T h i s statement i s v a l i d i n p r i n c i p a l f o r t h e bending v i b r a t i o n s ,
too,
The b r i d g i n g and t h e t e t r a h e d r a l t y p e v i b r a t i o n s o f t h e sub-
u n i t c l u s t e r models c a n be u s e d t o i n t e r p r e t t h e v i b r a t i o n a l
s p e c t r a o f an a c t u a l z e o l i t e . The a p p r o x i m a t e a s s i g n m e n t t h u s
o b t a i n e d i s shown i n T a b l e 4. So t h e h i g h f r e q u e n c y framework
a b s o r p t i o n s can be a s s i g n e d t o a s y m m e t r i c b r i d g i n g s t r e t c h i n g
vibrations. The m a i n p a r t o f p o t e n t i a l e n e r g y o f t h e s e i s l o -
c a t e d i n t h e S i O bonds. Then f o l l o w a s y m m e t r i c b r i d g i n g s t r e t c h -
i n g v i b r a t i o n s w i t h dominant A 1 0 c h a r a c t e r ( S i O c h a r a c t e r less
t h a n 10%). Symmetric b r i d g i n g and t e t r a h e d r a l v i b r a t i o n s a p p e a r
a t l o w e r f r e q u e n c i e s . The d o u b l e r i n g and p o r e o p e n i n g modes
m e n t i o n e d i n T a b l e 4 have been d e s c r i b e d i n d e t a i l e l s e w h e r e
(ref. 1 7 ) . The a b s o r p t i o n s between 510 cm" and 408 cm" c a n be
Cluster C a l c u l a t e d f r e q u e n c y r e g i o n and a p p r o x i m a t e a s s i g n m e n t
Si04 / A104 1011-978 828-805 720 574
V (SiO) Ztt,as(AIO) Vt,s(SiO) 2r (A10)
t,as t.s
03S i - C ( i ) - A 1 0 3 1086-1041 1C16-982 845-811 820-803
Y
b, a s
(Si0,AlO) 5 ,a s ( S i O ) yt ,as (A10) 4, ( S i o ,A10) 5,705-690
( s i o Ale)
8
571-559 239-231
v (A10) Y (A10,SiO)
T, s b, S
6R(hP) 1082-1052 991 866-864 827 785 756
b, a s ( S i O . A l 0 ) Y,as(SiO) v, %,as (A1O) 5,a s (A1o) vb, as (A1O)
I 6R(hP)
06 R
.
590-549
dbb (OT0)
219,136-114
524-503
dtb, (OT0)
481-397
am
353-351.214-162
Jm
325-222
atb, a s
abb. a s
I
( t t * t b and bb c h a r a c t e r i z e a n g l e d e f o r m a t i o n s . i f t h e a n g l e c o n s i s t s o f two t e r m i n a l ( t t ) .
o f a t e r m i n a l a n d a b r i d g i n g ( t b ) a n d of two b r i d g i n g bonds ( b b ) ; s and a s d e n o t e symmet-
r i c a l and a s y m m e t r i c a l d e f o r m a t i o n s , respectively; OTO=OA10, O S i O ; m c h a r a c t e r i z e s mixed
v i b r a t i o n a l nodes)
518
a s s i g n e d t o OTO b e n d i n g s . I t s h o u l d be n o t e d t h a t so f a r an ex-
p l a n a t i o n o f t h e e x p e r i m e n t a l s p e c t r a c a n be o b t a i n e d o n l y by
c o n s i d e r i n g t h e v i b r a t i o n a l b e h a v i o u r o f some d i f f e r e n t s u b u n i t
c l u s t e r models,
TABLE 4
Approximate assignment o f observed v i b r a t i o n a l f r e q u e n c i e s o f
NaX z e o l i t e ( S i / A l = l . l 2 )
cm-' Assignment a )
obs.
IF! b, RA
1082 m
1078 sh
985 m
975 ve
800 w
(A10)
752 m b,as
700 m ub, ( S i 0 , A l O )
612 vw vl-s(AIO)
562 m d o u b l e r i n g mode
510 vs 'bb,
461 S
$( OTO )
408 W
375 m
p o r e o p e n i n g mode
364 m
As a r e s u l t t h e FLANIGEN c o n c e p t i o n o f e x t e r n a l and i n t e r n a l
t e t r a h e d r a l v i b r a t i o n s h a s t o be m o d i f i e d because o f t h e s t r o n g
c o u p l i n g between t h e z e o l i t e framework v i b r a t i o n s . Each bond has
b r i d g i n g and i n t e r n a l t e t r a h e d r a l c h a r a c t e r s i m u l t a n e o u s l y . Si-
m i l a r c c n c l u s i o n s have been drawn by WALTHER ( r e f s . 18,19) from
c o r r e s p o n d i n g c a l c u l a t i o n s f o r ZSM-5 z e o l i t e s u b u n i t c l u s t e r
models. The c o u p l i n g between t h e t e t r a h e d r o n s d o m i n a t e s t h e
c o u p l i n g w i t h i n t h e t e t r a h e d r o n s . T h e r e f o r e we p r e f e r t o d i s -
519
t i n g u i s h between l o c a l i z e d and d e l o c a l i z e d v i b r a t i o n s ( s e e
ref. 20) t h a n between i n t e r n a l and e x t e r n a l ones.
CONCLUDING REMARKS
Z e o l i t e s r e p r e s e n t an e x t r a o r d i n a r y c h a l l e n g e f o r t h e v i b r a -
t i o n a l s p e c t r o s c o p y because o f t h e i r l a r g e u n i t c e l l s . They a r e
c o n n e c t e d w i t h a l a r g e number o f v i b r a t i o n a l modes l y i n g c l o s e l y
t o g e t h e r i n a s m a l l frequency region. Vibrational calculations
o f z e o l i t e s u b u n i t c l u s t e r models c a n be a c c o u n t e d f o r an i n t e r -
mediate step i n t r e a t i n g t h e complete s p e c t r o s c o p i c a l l y s i g n i f i -
cant u n i t c e l l . I f t h e c l u s t e r p r o b l e m w i l l be s o l v e d , the
q u e s t i o n f o r a p p r o p r i a t e f o r c e f i e l d s r e m a i n s open. In a d d i t i o n
t o t h i s methods f o r t h e e s t i m a t i o n o f v i b r a t i o n a l i n t e n s i t i e s o f
z e o l i t e s seem t o be n e c e s s a r y e x p l a i n i n g c o m p l e t e l y t h e e x p e r i -
m e n t a l s p e c t r a . W i t h r e s p e c t t o b o t h t h e problems mentioned
above quantum c h e m i c a l methods have t o c o n t r i b u t e c o n s i d e r a b l y .
REFERENCES
B. MULLER
I n s t i t u t f u r P h y s i k a l i s c h e Chemie, Friedrich-Schiller-Universitat
Jena. LessingstraRe 10, 0-6900 Jena, BRD
SUMMARY
I t i s shown t h a t z e o l i t e s can be c h a r a c t e r i z e d and c l a s s i f i e d
by means o f t o p o l o g i c a l s t r u c t u r e a n a l y s i s . The t o p o l o g y used i s a
non-metrical geometry. The advantage o f u s i n g t h e s e t o p o l o g i c a l
s t r u c t u r e d e s c r i p t i o n i s t h a t t h e general s t r u c t u r a l p r o p e r t i e s
r e p r e s e n t i n g t h e frame f o r t h e p h y s i c s and c h e m i s t r y o f m a t e r i a l s
can be d e c l a r e d w i t h s i m p l e numbers o f t h e t o p o l o g i c a l parameters
Nk1. The l o c a l r e c i p r o c a l curves o f t h e c e l l u l a r c o n f i g u r a t i o n
b31/l11, expressed i n t h e t o p o l o g i c a l parameters, a r e measures f o r
both t h e compactness and t h e c a t a l y t i c a l p r o p e r t i e s o f z e o l i t e s .
The general s t r u c t u r e f u n c t i o n N 2 1 = N21(NS2,NO',N12) o f t h e
independent t o p o l o g i c a l parameters N k 1 i s deduced f r o m t h e t h e o r y
of c e l l u l a r configurations. The d i s t r i b u t i o n f u n c t i o n s g21i and
9 3 2 1 o f t h e f a c e s and polyhedra, r e s p e c t i v e l y , which may b u i l d up
t h e v a r i e t y o f z e o l i t e c o n f i g u r a t i o n s , a r e given.
INTRODUCTION
The simplest, but a l s o t h e most e s s e n t i a l relations between
e 1ement s of spatial systems a r e o f a topological nature. The
topo 1ogy obtains the connective s t r u c t u r e relations which are
i n v a r i a n t a t continuos transformations (ref. l), therefore, the
topo 1ogy s non-metrical. The problem o f s p a t i a l t o p o l o g i c a l s t r u c -
ture ana y s i s consists i n the determination of both intrinsic
t o p o l o g i c a l s t r u c t u r e elements and i n t h e corresponding connective
relations between those c o n s t r a i n e d t h e structure configurations
(refs. 2,3). Atomic condensed systems such as z e o l i t e s may be
uniquely mapped into space-filling cellular configurations
(ref .4).
One k-celloid of t h e dimension k correponds inquely to one
structure element o f t h e concrete zeolite. These homomorphisms
make it p o s s i b l e f o r t h e t o p o l o g i c a l parameters o f the cellular
configurations space t o u n i q u e l y r e p r e s e n t , as w e l l as classify,
t h e t o p o l o g i c a l s t r u c t u r e o f atomic condensed system ( r e f . 5). The
topological parameters Nk1 and t h e i r d i s t r i b u t i o n functions gkli
constrain n o t o n l y t h e s p a t i a l c o n f i g u r a t i o n and arrangement but
also the s p a t i a l e x i s t e n c e and s t a b i l i t y i n every cellular-con-
nected system represented b y t h e z e o l i t e s ( r e f . 6 ) .
522
i=l i=l
TABLE 1
The t o p o l o g i c a l p a r a m e t e r s o f t h e z e o l i t e s
Moreover, t h i s t a b l e 1 a l s o shows t h e t o p o l o g i c a l i n t r i n s i c r a t i o
between t h e numbers o f p o l y h e d r a end v e r t i c e s N 3 / N 0 , the recipro-
526
TABLE 2
P o s s i b l e face d i s t r i b u t i o n s F Z 1 1 o f a t y p i c a l p o l y h e d r o n w i t h N j 2
= 10 f o r t h e t o p o l o g i c a l parameters NO1 4, N1z = 3, and N21 =
4.8, r e s p e c t i v e l y
_ _
;F21i\n21i 1 3 4 5 6 7 8 9 10 1
I
I \ 1 - 1
I
1 1 1 0 2 8 0 0 0 0 0 1
1 2 : 1 0 9 0 0 0 0 0 1
; 3 1 0 3 6 1 0 0 0 0 1
I
1 4 I 1 1 7 1 0 0 0 0 1
1 5 1 0 4 4 2 0 0 0 0 :
1 6 1 1 2 5 2 0 0 0 0 1
1 7 I 2 0 6 2 0 0 0 0 1
1 8 1 0 5 2 3 0 0 0 0 1
I
! 9 I 1 3 3 3 0 0 0 0 :
f 10 1 2 1 4 3 0 0 0 0 1
1 11 1 0 6 0 4 0 0 0 0 1
: 12 1 1 4 1 4 0 0 0 0 1
1 13 1 2 2 2 4 0 0 0 0 1
1 14 1 3 0 3 4 0 0 0 0 1
1 15 : 2 3 0 5 0 0 0 0 :
1 16 1 3 1 1 5 0 0 0 0 1
:
I
17 : 4 0 0 6 0 0 0 0 :
I
I I
Toml-ogicpl curvatures o f z e o l i t e c o n f i g u r a t i o n s
The mean topological reciprocal u n i t curvature b311/vl i 1 is
characteristic o f the adsorption properties o f the zeolites.
The mean reciprocal configuration curvature i s found in the
range 2.667 <. b311/v1,1 < 4.5 (table 1 ) . I n t h e case of single
polyhedra, the range i s g r e a t e r 1.0 < bJ*l/vl.l 4.5 (table 11,
as f o r F a u j a s i t e .
The g r e a t e r t h e polyhedron v a l u e o f b3*l/vlpl, t h e more e a s i l y
l a r g e molecules can be adsorbed a t t h e polyhedra. The s m a l l e r the
configuration value of bJ.l/vl.l the better a force-field of
curvature i s g i v e n which can be bent and can break t h e molecules.
The c a t a l y t i c a l p r o p e r t i e s of t h e z e o l i t e s e s s e n t i a l l y give rise
to both t h e mean r e c i p r o c a l u n i t c u r v a t u r e o f the configuration
and those o f t h e s i n g l e polyhedra.
The value of bJ.l/vl ~1 for zeolite configurations must be
g r e a t e r than 8/3. Those i s a measure f o r t h e d i s c r i m i n a t i o n o f t h e
zeolites. The m o d i f i c a t i o n s o f b o t h S i O z and f e l s p a r s have values
f o r r e c i p r o c a l c u r v a t u r e s l e s s t h a n 8/3.
The p o s s i b l e polyhedron d i s t r i b u t i o n n32i o f z e o l i t e configura-
t i o n s are given i n r e f . 7 .
The number o f polyhedra per v e r t e x N3/N0 i s also characteristic
528
REFERENCES
1 H . S . M . Coxeter, Unvergangliche Geometrie, B i r k h b u s e r , Base1 1982
2 F. Yonezawa, T . Ninomiya ( E d s . ) , T o p o l o g i c a l D i s o r d e r i n Conden-
sed M a t t e r , S p r i n g e r , B e r l i n , 1983
3 N.J. T u r r o , Angew. Chem., 98 (1986) 872-879
4 8 . Mullet-. Exper. Tech. Phys., 36 (1988) 121-134
5 B. M u l l e r , The t o p o l o g i c a l c h a r a c t e r i z a t i o n o f amorphous s t r u c -
t u r e s , i n P h y s i c a l Research, Akademie-Verlag, B e r l i n 1990
6 D. Stoyan, W.S. K e n d a l l . R . Mecke, S t o c h a s t i c Geometry, Akade-
mie-Verlag, B e r l i n 1987
7 B. M u l l e r , The t o p o l o g i c a l f o u n d a t i o n s o f s t r u c t u r e c h e m i s t r y ,
submitted f o r p u b l i c a t i o n
8 R. Schubert, B. M i l l l e r , Computing Program NWS, Computer Centre
o f Friedrich-Schiller-Unioversity Jena, 1987
9 0. M u l l e r , R . Schubert. Exper. Tech. Phys. 36 (1988) 135-144
10 B. Moller, R . Schubert, Wiss. Z e i t s c h r . F r i e d r . - S c h i l l e r - U n i v .
Jena, i n p r e s s
11 W.W. Meier, D.H. Olsen, A t l a s o f Z e o l i t e S t r u c t u r e Types,
B u t t e r w o r t h s , London, 1987
C,. Ohlrnann et nl. (Editors),Culalysk and Adsorption by Zeolites 529
1991 Elsevier Science PublishersR.V.,
Amsterdam
SUMMARY
The secondary synthesis on modified pentasil zeolites and Its
influence on the properties of these zeolites was investiga-
ted. It is shown by X-ray diffractiontZ7Al MAS NMR and nitrogen
adsorption that a high degree of dealumination and a high pH
value of the synthesis mixture led to a favourable insertion of
aluminium into the ZSM-5 framework.
INTRODUCTION
In connection with the industrlal application of zeolites a
rapid development in the processes of chemical conversion, sepa-
ration and cleaning can be observed. Unmistakable is the increa-
sing importance of new zeolitic molecular sieves with adapted
pore systems and defined surface-chemical properties.
one way for the production of such zeolites is the isomor-
phous substitution of aluminium and/or silicon in the framework
through other elements with the condltions of the hydrothermal
crystallization. A high variation concerning the multitude of
various elements was observed for the pentasil zeolites (ref.
1). However, the information about the state of these elements
In the zeolitic framework is limited.
The actual investigations have shown that such materlals are
also available as a result of the secondary synthesis using alu-
minosilicates (refs. 2 , 3 ) . The secondary synthesis is a new and
almost unknown procedure for the postsynthetic zeol te modifice-
tion. This procedure allows the reversion of the dealuminina-
tion of zeolltes, observed during their use, by a s mple method
(ref. 4 ) .
The aim of this paper is to show the systematical investiga-
tions of the secondary synthesis of modified pentasils to get
informations concerning the influence of the conditions of syn-
thesis on the structural, surface-chemical and adsorptional pro-
perties of the resulting zeolites.
EXPERIMENTAL
Materials and Methods
The starting material ZSM-5 (Si/A1=50) synthesized with or-
ganic template (ref. 5) was calcinated f o r 6 hours at 700 " C t
800 Oc and 900 OC. One part of the these samples was transrered
into the H-form, where 25 g of the freshly calcinated zeolite
powder was ion exchanged wlth 1 1 of 0.5 M aqueous solution of
ammonium nitrate ( 3 hrs, 80 "C) and deammoniated ( 4 hrs, 500
0
C) .
For the secondary synthesis with aluminium insertion alumini-
um sulphate was contacted with the zeolite and an aqueous solu-
tion of 2 N NaOH where the atomic ratio of aluminium between the
zeollte and the suspension was varied. The reaction mixture with
pH 10 to 12 was stirred for 3 hours at 70 O C , filtered and
washed carefully. The resulting products were dried and charac-
terized by various analytical methods.
The determination of the Si/A1 ratios (ref. 6) of the samples
was carried out at a NMR pulse spectrometer designed at the KMU
Leipzig at a resonance rrequency of 70 MHz. The chemical shltt
against [A1(H20)6]3+ was obtained with an accuracy of 2 ppm.
The identification of the crystalline phases and the crystal-
linity of the samples were determined by means or a goniometer
HZG 4 in the 20 region from 5 to 70 '. For comparlson the crys-
tallinity of the Leuna-ZSM-5 standard was used. The volumes of
the unit cells of some zeolites were obtained from the difreren-
ces of the angel positions of 5 references in the 20 range from
23.00 to 25.70 in comparison to the references of a-A1203.
The adsorption properties were investigated by the measure-
o
ments of the nitrogen isotherms at - 196 C on a Sartorius ba-
lance.
The designation, the conditions of the secondary synthesis,
the aluminium content per unit cell. the Sl/Al ratios, the crys-
tallinity, the volume of the unit cell from X-ray data and the
nitrogen adsorption capacity at 0.1 MPa are shown in table 1.
531
TABLE 1
Characterization of the ZSM-5 zeolites investigated
2 7 ~ 1MAS N M R
Dealuminated samples
The sharp signal in the 27Al MAS NMR spectra at 53 ppm was
assigned to the tetrahedrically coordinated aluminium in frame-
work positions. The higher the calcination temperature the lower
the intensity of the signal which is due to the dealumination of
the framework. In fig. 1 the change of the amount of aluminium
2.0 .
u t
Fig. 1 Change of the
? 1.6-
A
amount of aluminium
6
1.2 - per unit cell in de-
pendence on the cal-
0.8 - cination temperature
0.1, - (A:NaZSM-5, B:HZSM-5)
700 800 - 9 0 0
T("C1
per unit cell is demonstrated by the dependence on the calcina-
tion temperature. It is shown that in the case of HZSM-5 zeoli-
tes the dealumination of the framework with higher temperatures
becomes advantageous in comparison with NaZSM-5 zeolltes.
Realuminated samples
The results of the realumination of the calcinated NaZSM-5 zeo-
lltes are shown in fig. 2. In all cases the pH of the aqueous
A
Fig. 2 Realumination in
dependence on the calci-
nation temperature and
the Al-Supply at pH=12
( theor. max. values A :
I
700 800 -900
T ("C 1
10-
u t
< 8-
d
6-
L-
2-
10 11 -
PH
12 150- 50
d(PPm1
-50
Nitrogen Adsorption
Now we should focus our attention on the influence of the
chemical reactions of the solid on the pore system of the post-
synthezised zeolites. The investigations have shown that in all
535
ACKNOWLEDGEMENTS
The authors thank Dr. P. Kraak and K. Heimbach for supplying
the X-ray data and Prof. D. Freude and Dr. K. Becker for helpful
support.
REFERENCES
M . Tielen, M . Geelen and P.A. Jacobs, Proc. Intern. Symp.
Zeolite Catal., szeged 1985, Acta Phys. Chem. Szeged., 1985,
P. 1
G.W. Skeels and E.M. Flanigen, ACS Symposium series ( M . L .
Ocelli and H. E. Robson, Eds.) 398 (1989) 420
B. Sulikowskl and J. Klinowski. ACS Symposioum Series ( M . L .
Ocelli and H.E. Robson, Eds.) 398 (1989) 393
I
1 1 1 3
BI Z j b r o w i u s , E. Loffler , G. Finger , E. Sonntag', M. Hunger
4
and J . Kornatowski
' C e n t r a l I n s t i t u t e o f P h y s i c a l Chemistry and 'Central I n s t i t u t e o f
I n o r g a n i c Chemistry o f t h e Academy o f Sciences o f t h e GDR,
Rudower Chaussee 5, B e r l i n , DDR-1199 (German Democratic R e p u b l i c )
'Department o f Physics, K a r l - M a r x - U n i v e r s i t y L e i p z i g , L i n n s s t r . 5,
L e i p z i g , DDR-7010 (German Democratic R e p u b l i c )
4 1 n s t i t u t e o f Chemistry, N i c o l a u s Copernicus U n i v e r s t y , Gagarina
7 , 87-100 Torun (Poland)
SUMMARY
SAPO-5 was s y n t h e s i z e d from s t a r t i n g g e l s COVI - r i n g a broad
range o f composition. The i n c o r p o r a t i o n o f s i l i c o n i n t o t h e A F I
framework was s t u d i e d by m u l t i n u c l e a r MAS NMR and I R spectroscopy.
I t was found t h a t t h e g e l composition determines t h e morphology o f
t h e c r y s t a l s , b u t o n l y s l i g h t l y i n f l u e n c e s t h e amount o f s i l i c o n
i n c o r p o r a t e d . An upper l i m i t f o r t h e i n c o r p o r a t i o n o f i s o l a t e d
s i l i c o n atoms can be expected.
INTRODUCTION
C r y s t a l l i n e s i l i c o a l u m i n o p h o s p h a t e m o l e c u l a r s i e v e s (SAPOs) a r e
novel microporous s o l i d s which can be considered as derivatives
from t h e corresponding alurninophosphates by isomorphous s u b s t i t u -
tion (ref. 1). D i f f e r e n t mechanisms f o r t h i s s u b s t i t u t i o n a r e d i s -
cussed. Only i n t h e case o f an i n c o r p o r a t i o n o f monomeric s i l i c o n
on phosphorus s i t e s ( i . e . t h e s i l i c o n atoms a r e bonded v i a oxygen
to four adjacent aluminium atoms), the calcination of the as-
synthesized SAP0 generates one Bronsted a c i d i c s i t e per one s i l i -
con atom incorporated. Therefore, not only the o v e r a l l content,
b u t a l s o t h e t y p e o f s i l i c o n i n c o r p o r a t i o n determines t h e c a t a l y -
t i c a c t i v i t y o f SAPOs.
The goal o f our work was t o i n v e s t i g a t e t h e influence o f gel
composition on the final composition of the crystals and, in
p a r t i c u l a r , on t h e s i l i c o n i n c o r p o r a t i o n i n t o t h e framework o f t h e
resulting differently s i z e d and shaped SAPO-5 crystals. Further-
more, we want t o show t h a t t h e combination o f NMR and I R s p e c t r o -
538
EXPERIMENTAL
Synthesis
0
SAPO-5 sample were s y n t h e s i z e d h y d r o t h e r m a l l y a t 190 C s t a r t i n g
from g e l s o f d i f f e r e n t molar r a t i o s o f t h e components a A1 0 .
2 3
b P205 c TEA . d Si02 . e H 2 0 ( c f . Table 2 ) . The g e l s were
formed applying an aluminiumoxydehydrate s o l (2.35 mass% A 1 0 1,
2 3
phosphoric a c i d ( 8 5 mass% H PO 1, t r i e t h y l a m i n e (TEA) a c t i n g as
3 4
template, a s i l i c a s o l ( 4 0 mass% S i O ) , and b i d i s t i l l e d w a t e r . The
2
s t a r t i n g pH value o f t h e g e l was 3.3 !: 0 . 2 r i s i n g t o about 7.0
after completion of the crystallization process. The obtained
c r y s t a l s were separated f r o m t h e mother l i q u o r and, i f necessary,
from some o c c a s i o n a l l y formed s m a l l amount o f by-products, washed
0
c a r e f u l l y and d r i e d . C a l c i n a t i o n was performed under a i r a t 750 C .
A more d e t a i l e d d e s c r i p t i o n o f t h e s y n t h e s i s i s g i v e n i n r e f . 2.
Chemical a n a l y s i s
..____~___
,
'..
, I
539
1-nst r ument a 1
The 27Al, 29Si and 31P MAS NMR s p e c t r a were recorded on a
Bruker MSL 400 spectrometer. The experimental conditions f o r the
NMR measurements a r e summarized i n Table 1 . A l l s p e c t r a shown i n
t h i s paper were o b t a i n e d by s i n g l e p u l s e e x c i t a t i o n . I n t h e case
o f 2 9 S i and 31P MAS NMR, high-power p r o t o n d e c o u p l i n g was a p p l i e d .
The chemical shifts reported for 27Al are not corrected for
second-order quadrupole e f f e c t s .
'H MAS NMR s p e c t r a were measured a t room temperature u s i n g a
Bruker MSL 300 spectrometer and a home-made magic-angle-spinning
equipment t h a t a l l o w s t o s p i n sealed g l a s s ampoules. The total
c o n c e n t r a t i o n o f OH groups i n t h e a c t i v a t e d samples was determined
by comparing t h e l i n e i n t e n s i t y w i t h t h a t o f a standard.
TABLE 1
Experimental c o n d i t i o n s f o r MAS NMR measurements.
____- -
nucleus resonance p u l s e flip repeti- no. o f MAS reference
frequency d u r a t i o n angle t i o n t i m e scans f r e q u .
/MH i! /us /S /kHz
1
H 300.0 4.0 7r/2 10.0 400 2.5 TMS
3+
2 7 ~ 1 104.2 0.6 T/l2 0.5 800 5.1 Al(H20)6
RESULTS AND D I S C U S S I O N
By means o f XRD i t was proven t h a t all samples investigated
e x h i b i t indeed A F I s t r u c t u r e ( r e f . 4 ) . The q u i t e d i f f e r e n t morpho-
logy o f t h e t h e c r y s t a l s i s i l l u s t r a t e d in ref. 2: sample A in
Fig. lA, samples B and D i n F i g s . 2D and 4 8 and sample C i n F i g .
4E. The chemical compositions o f b o t h t h e g e l s and t h e c a l c i n e d
samples a r e g i v e n i n Table 2. Although the compositions o f the
g e l s cover a broad range, t h e composition o f t h e SAPO-5 crystals
i s nearly c o n s t a n t .
TABLE 2
Chemical compositions o f b o t h t h e g e l s and t h e c a l c i n e d and
dehydrated samples.
samp 1 e ge 1 c a l c i n e d sample
A1 0 , : P 0 : S i O : TEA: H20 A1 : P : Si Al/(P+Si)
2 3 2 5 2
*
A- 1.0 : 1 . 0 3 : 0.25: 1.55: 300 0.506: 0.458: 0.036 1.024
31P A-29.4
. . -
100 50 0 -50 0 -20 -Ul -GO
PPm PPm
'95i M A S N M R DRIFT
RL I
29si M A S NMR O R I FT
- 95.6
I
3625 A 3520
-
~~
3.8
I
4.8
I
*
I
*
* *
1
Fig. 4. H MAS NMR spectrum o f SAPO-5 (sample A ) .
TABLE 3
Concentrations o f s i l i c o n atoms and h y d r o x y l groups.
~ _ _ _ _ ~ _ _ _ _ __~ _________-__---_____--
~ ~
a
sample s i l i c o n atoms b r i d g i n g OHb n o n - a c i d i c OHC
/1O2O g-1 /1O2O g-l /1O2O g-1
~ - ._.. __ -
~ ... .----
,-
,I
- 95.4
I
3625 1 13520
I 1 I , L
29 .
Fig. 5 . S i MAS NMR and DRIFT s p e c t r a o f t h e by-product ( b r o k e n
l i n e s ) and t h e SAPO-5 phase ( s o l i d l i n e s ) o b t a i n e d f r o m t h e same
synthesis batch a f t e r c a l c i n a t i o n .
100 0 -100
PPm
F i g . 6 . 2 7 A l M A S NMR s p e c t r a o f t h e b y - p r o d u c t :
( a ) as-synthesized and ( b ) c a l c i n e d and d e h y d r a t e d .
Concerning the chemical nature o f the by-product, we assume
t h a t i t i s an aluminophosphate. T h i s i s n o t o n l y supported by t h e
I R spectrum i n F i g . 5, where bands due t o A l O H and POH a r e p r e -
sent, b u t a l s o by 2 7 A l and 31P MAS NMR. The l i n e p o s i t i o n i n t h e
2 7 A l MAS NMR spectrum o b t a i n e d f o r t h e u n c a l c i n e d by-product (Fig.
6) i s characteristic of aluminium i n o c t a h e d r a l oxygen c o o r d i n a -
t i o n i n an aluminophosphate ( r e f . 1 8 ) . During c a l c i n a t i o n , t h e oxy-
gen c o o r d i n a t i o n i s changed i n t o a t e t r a h e d r a l one r e f l e c t e d by a
characteristic l i n e position a t 37.5 ppm. We f a i l e d t o a s s i g n t h e
by-product t o any known aluminophosphate s t r u c t u r e by XRD.
CONCLUSIONS
Morphology and s i z e of t h e SAPO-5 c r y s t a l s can be c o n t r o l l e d by
t h e composition o f t h e s t a r t i n g g e l .
For t h e c r y s t a l l i z a t i o n procedure used, a predominant monomeric
incorporation o f silicon i s achieved f o r q u i t e d i f f e r e n t c r y s t a l
morphologies. We1 1-shaped SAPO-5 crystals containing up to 4%
s i l i c o n on h y p o t h e t i c a l phosphorus T s i t e s can be synthesized.
An upper l i m i t for monomeric incorporation of silicon into
SAPO-5 can be expected. Above t h i s limit, only the fraction of
s i l i c o n present i n s i l i c a - r i c h islands w i t h i n the structure (and/
o r i n amorphous m a t e r i a l ) i s i n c r e a s i n g .
The s t r u c t u r a l changes caused by t e m p l a t e removal and by rehy-
d r a t i o n are n o t s i g n i f i c a n t l y i n f l u e n c e d by t h e incorporation o f
s i 1 icon.
A sometimes o b t a i n e d by-product o f t h e s y n t h e s i s was shown t o
be an aluminophosphate w i t h o u t s i l i c o n .
REFERENCES
1 E.M. F l a n i g e n , R.L. P a t t o n and S . T . Wilson, i n : P.J. Grobet,
W.J. M o r t i e r , E . F . Vansant and G. S c h u l z - E c k l o f f ( E d s . ) ,
I n n o v a t i o n i n Z e o l i t e M a t e r i a l Science, E l s e v i e r , Amsterdam,
1988, pp. 13-28.
2 G. F i n g e r , J . Kornatowski, J . Richter-Mendau, K . Jancke,
M. Bulow and M. Rozwadowski, t h i s volume.
3 C . Peuker, G. F i n g e r , E. L o f f l e r and W . P i l z , i n p r e p a r a t i o n .
4 W.M. Meier and D.H. Olson, A t l a s o f Z e o l i t e S t r u c t u r e Types,
2nd. edn., B u t t e r w o r t h s , London, 1987.
5 D. M u l l e r , E. Jahn, B. Fahlke, G. Ladwig and U . Haubenreisser,
Z e o l i t e s , 5 (1985) 5 3 - 5 6 .
548
SUMMARY
A l P O -14 was prepared u s i n g p i p e r i d i n e as t e m p l a t i n g agent. The
4
XRD and MAS NMR r e s u l t s i n d i c a t e s i g n i f i c a n t s t r u c t u r a l changes o f
t h i s aluminophosphate d u r i n g template removal and r e h y d r a t i o n . The
l a t t i c e parameters o f t h e as-synthesized as w e l l as t h e c a l c i n e d
and dehydrated form o f A l P O -14 were determined f r o m X-ray powder
4
d i f f r a c t i o n d a t a . The l a t t i c e parameters o f t h e c a l c i n e d samples
correspond t o t h e i d e a l i z e d geometry suggested f o r A1P04-14, b u t
which has n o t y e t been a c t u a l l y observed. From 31P MAS NMR t h e
e x i s t e n c e o f a t l e a s t t h r e e non-equivalent phosphorus s i t e s i n t h e
c a l c i n e d form o f A l P O -14 i s d e r i v e d .
4
INTRODUCTION
The s y n t h e s i s and c h a r a c t e r i z a t i o n o f microporous c r y s t a l l i n e
aluminophosphates (A1P04-n (ref. 1) ) has a t t r a c t e d much i n t e r e s t
d u r i n g t h e l a s t few years. Because o f t h e i r s t r u c t u r a l and compo-
sitional diversity, A l P O -based m o l e c u l a r s i e v e s can be t a i l o r e d
4
t o many d i f f e r e n t processes. Only some o f t h e AlPO t y p e m a t e r i a l s
4
have framework t o p o l o g i e s i d e n t i c a l w i t h those o f known z e o l i t e s .
Among t h e huge number o f newly s y n t h e s i z e d A1P04 t y p e s , there are
some m a t e r i a l s which have been p a t e n t e d a c c o r d i n g t o their XRD
patterns, b u t l i t t l e i s known about t h e i r s t r u c t u r e s and proper-
ties.
The goal of the present study was to characterize A1P04-14
(ref. 2) by XRD, solid state NMR as w e l l as thermoanalytical
measurements. The structure type of as-synthesized A1P04-14 is
presumed t o be t h a t o f a g a l l i u m phosphate s y n t h e s i z e d by means o f
iso-propylamine (refs. 3,4). A r e f i n e m e n t o f t h e A1P04-14 struc-
t u r e has n o t y e t been p u b l i s h e d .
550
EXPERIMENTAL
Sample p r e p a r a t i o n
As d i s t i n c t from t h e U.S. patent ( r e f . 2), the synthesis o f
A l P O -14 was performed n e i t h e r w i t h t - b u t y l a m i n e n o r w i t h i s o -
4
propylamine, b u t w i t h p i p e r i d i n e as t h e t e m p l a t i n g agent. The f o l -
l o w i n g procedure was used: 13 g o f water, 6.6 g o f p h o s p h o r i c a c i d
(85 mass%) and 2.8 g o f pseudoboehmite ( 7 4 mass% A 1 2 0 3 , 2 6 mass%
H 0 ) were mixed by v i g o r o u s s t i r r i n g . After addition of 4 g of
2
p i p e r i d i n e t h e f i n a l c o m p o s i t i o n o f t h e r e a c t i o n m i x t u r e was
Concerning t h e chemical c o m p o s i t i o n o f t h e c a l c i n e d A l P O
crys-
4
tals, the A l / P r a t i o was found t o be 1 : 1 b o t h i n t h e b u l k phase
(chemical a n a l y s i s ) and i n t h e s u r f a c e l a y e r s (XPS).
Instrumental
Crystal habit and size were ascertained using a scanning
e l e c t r o n microscope TESLA BS300 w i t h p l a t i n u m coated specimens.
The X-ray powder diffraction p a t t e r n s were recorded using a
G u i n i e r f i l m camera (CuK r a d i a t i o n ) , a high-temperature G u i n i e r
Crl
camera and a diffractometer with Bragg-Brentano geometry (CuK
CI
radiation).
The thermal analyses (DTA and TG) were carried out using a
Derivatograph supplied by MOM, Budapest. Samples (200 mg) s a t u -
r a t e d w i t h water a t room temperature were heated f r o m 293 K to
1073 K a t a r a t e o f 5 K/min. For DTA measurements, 0 - A 1 0 powder
2 3
was used as t h e r e f e r e n c e m a t e r i a l .
The magic angle s p i n n i n g (MAS) NMR s p e c t r a were recorded on a
Bruker MSL 400 spectrometer. The 2 7 A l NMR s p e c t r a were o b t a i n e d a t
a resonance frequency o f 104.2 MHz and a s p i n n i n g r a t e o f 5 . 3 kHz.
S i n g l e p u l s e e x c i t a t i o n (SPE) w i t h n/12 p u l s e s o f 0.6 p s length
was used. The l i n e positions are reported r e l a t i v e t o A l C l in
3
551
a = 9.697(2) 6 CI 74.92(2)'
b 9.947(2) p 75.14(2)' V = 953.6 A3
c = 10.612(2) A y 89.40(2)'.
a = 14.059(6) A
b = 13.480(8) A I; = 107.30(4)' v = 1850.8 a3
c 10.229(4) a.
These l a t t i c e parameters correspond t o t h e i d e a l i z e d geometry o f
t h e A l P O -14 s t r u c t u r e t y p e as d e s c r i b e d i n r e f . 4, b u t which have
4
n o t y e t been a c t u a l l y observed.
The m o n o c l i n i c c e l l o f t h e c a l c i n e d A l P O -14 i s r e l a t e d t o t h e
4
u n i t c e l l o f t h e as-synthesized form. T h i s may be seen a f t e r an
axial transformation o f the l a t t i c e parameters o f t h e C-centred
m o n o c l i n i c c e l l t o t h a t o f a p r i m i t i v e t r i c l i n i c one a c c o r d i n g to
-t
a =
-t
+ %mon ) / 2 , +btr = +
(amon
- +bmon)/2 .)
and ctr = c
+ . The
tr (amon mon
r e s u l t i n g reduced t r i c l i n i c c e l l has t h e f o l l o w i n g parameters:
a = 9.739 A a = 77.60'
b = 9.739 A 0 77.60'
c = 10.229 6 Y 87.59'.
We suppose t h a t s i m i a r t o t h e d i s t o r t on o f t h e i d e a l geometry
o f t h e framework by t h e t e m p l a t e i n t h e as-synthesized form, the
a d s o r p t i o n o f water leads t o one o r even more r e l a t e d s t r u c t u r e s
w i t h reduced symmetry. T h i s assumption would be i n l i n e w i t h t h e
r e s u l t s o f t h e s o l i d s t a t e NMR f o r t h e c a l c i n e d and f u l l y rehydra-
t e d sample.
t h i s f o l l o w s from t h e comparison o f t h e t h e r m o a n a l y t i c a l d a t a w i t h
those of the elementary analysis. Water can be eliminated in
vacuum, and t h e weight l o s s a t 773 K amounts t o 9 %. A f t e r vacuum
t r e a t m e n t t h e endothermic peaks p r a c t i c a l l y vanish ( c f . F i g . 3).
The minor peak a t 403 K i s due t o t h e r e a d s o r p t i o n o f water d u r i n g
the handling o f t h e sample i n a i r (before the thermoanalytical
measurement).
820
’.....
T/K .---
The removal o f p i p e r i d i n e i i p o s s i b l e o n l y by d e g r a d a t i o n - in
a i r by o x i d a t i o n , i n argon by c r a c k i n g . The shape o f t h e DTA/TG
curves c o u l d be e x p l a i n e d assuming e i t h e r two p i p e r i d i n e s p e c i e s
t o be p r e s e n t o r a two-step behaviour f o r t h e d e g r a d a t i o n . From
t h e s y n t h e s i s c o n d i t i o n s (pH o f t h e g e l : ca. 3.6, a f t e r c r y s t a l l i -
+
zation: ca. 6.51, t h e f o r m a t i o n o f p i p e r i d i n i u m i o n s ((CH 2 ) 5 NH 2
i s probable ( r e f . 6 ) . On t h e o t h e r hand, t h e presence o f n e u t r a l
p i p e r i d i n e molecules was d e r i v e d f r o m t h e appearance o f the NH
wagging v i b r a t i o n band (720 ern-') i n t h e I R s p e c t r a ( r e f . 7).
556
'3c 23.0
45.8
-30.5
3’ P
-21.9
..*
-17.3
- L - - L - L
20 0 -20 -40 - 60
Ppm
CONCLUSIONS
Using p i p e r i d i n e as t e m p l a t i n g agent, we have s y n t h e s i z e d t h e
small pore molecular s i e v e A l P O -14 as a pure phase w i t h h i g h
4
crystallinity. On t h e b a s i s o f t h e presented XRD d a t a , an unambi-
guous assignment is possible. The topological equivalence of
GaPO -14 and A l P O -14 i s confirmed. Furthermore, t h e l a t t i c e para-
4 4
meters o f t h e c a l c i n e d and dehydrated f o r m correspond t o t h e idea-
lized geometry suggested for A l P O -14, but which has not Yet
4
a c t u a l l y observed.
From 31P MAS NMR spectroscopy it follows that there are at
l e a s t t h r e e non-equivalent phosphorus s i t e s i n t h e framework of
t h e c a l c i n e d f o r m o f A1P04-14.
The f o r m a t i o n o f occluded piperidinium ions during the syn-
t h e s i s i s supposed on t h e b a s i s o f t h e r m o a n a l y t i c a l d a t a and i s
c o r r o b o r a t e d by 1 3 C MAS NMR.
562
ACKNOWLEDGEMENT
We a r e i n d e b t e d t o D r . M. Hunger ( L e i p z i g ) f o r r e c o r d i n g
27Al MAS NMR s p e c t r a a t lower f i e l d .
REFERENCES
1 S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan and
E.M. F l a n i g e n , J. Am. Chem. SOC., 104 (1982) 1146-1147.
2 S.T. Wilson, B.M. Lok, and E.M. F l a n i g e n , U.S. P a t e n t
4,310,440 (1982).
3 J.B. P a r i s e , J . Chem. SOC., Chem. Commun., (1985) 606-607.
4 J.M. Bennett, W . J . D y t r y c h , J . J . P l u t h , J.W. Richardson and
J.V. Smith, Z e o l i t e s , 6 (1986) 349-361.
5 H . - 0 . K a l i n o w s k i , S. Berger and S. Braun, 13C NMR-Spektro-
skopie, Georg Thieme Verlag, S t u t t g a r t , 1984, p. 141.
6 E.M. F l a n i g e n , R . L . P a t t o n and S.T. Wilson, i n : P.J. Grobet,
W.J. M o r t i e r , E.F. Vansant and G. S c h u l z - E c k l o f f ( E d s . ) ,
I n n o v a t i o n i n Z e o l i t e M a t e r i a l Science, E l s e v i e r , Amsterdam,
1988, pp. 13-28.
7 B. Z i b r o w i u s , U. Lohse, E. A l s d o r f and J . Richter-Mendau,
J. Chem. SOC., Faraday Trans., i n p r e s s .
8 H . - 0 . K a l i n o w s k i , S. Berger and S. Braun, 13C NMR-Spektro-
s k o p i e , Georg Thieme Verlag, S t u t t g a r t , 1984, p. 323.
9 J . J . P l u t h , J.V. Smith and J.M. B e n n e t t , A c t a C r y s t a l l o g r . ,
C42 (1986) 283-286.
10 D. M u l l e r , I.Grunze, E. H a l l a s and G. Ladwig, 2 . anorg. a l l g .
Chem., 500 (1983) 80-88.
1 1 J.B. P a r i s e and C . S . Day, A c t a C r y s t a l l o g r . , C41 (1985) 515-
520.
12 U. Lohse, B. Z i b r o w i u s and J. Richter-Mendau, P o s t e r p r e s e n t e d
a t ZEOCAT 90
13 M. Goepper, F. Guth, L. Delmotte, J . L . Guth and H. K e s s l e r ,
i n : P.A. Jacobs and R . A . van Santen ( E d s . ) , Z e o l i t e s : F a c t s ,
F i g u r e s , F u t u r e , E l s e v i e r , Amsterdam, 1989, pp. 851-866,
14 K.J.D. MacKenzie, I . W . M . Brown, R.H. Meinhold and M.E. Bowden,
J. Am. Chem. SOC., 6 8 (1985) 293-297.
15 G. Blumenthal, G. Wegner, D. M u l l e r , A. Samoson and G. Kranz,
2 . anorg. a l l g . Chem., 576 (1989) 43-53.
16 D. M u l l e r , E. Jahn, G. Ladwig and U. Haubenreisser, Chem. Phys.
L e t t . , 109 (1984) 332-336.
17 W.F. Bleam, P.E. P f e f f e r and J.S. Frye, Phys. Chem. M i n e r a l s
16 (1989) 455-464.
18 B. Z i b r o w i u s and U. Lohse, u n p u b l i s h e d r e s u l t s .
19 T.M. Duncan and C . Dybowski, S u r f . S c i . Rep., 1 (1981) 157-250.
20 U. Lohse, M. Noack and E. Jahn, Ads. S c i . Techn., 3 (1986)
19-24.
G . Ohlrnann et al. (Editors),Catalysis and Adsorption by Zeolites 563
1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
INTRODUCTION
METHODS
NaY z e o l i t e s ( S i / A 1 = 2 . 4 5 ) w e r e d e a l u m i n a t e d b y r e a c t i o n w i t h a
flowing S i C 1 , vapour, a c c o r d i n g t o a procedure described elsewhere
( r e f . 4 ) . Samples, having a range of S i / A 1 r a t i o s , were p r e p a r e d by
r e a c t i n g 30 g of t h e p r e t r e a t m e n t z e o l i t e w i t h S i C l , / N , a t t e m p e r a t u r e s
r a n g i n g from430-723 K f o r 4 0 m i n . The z e o l i t e s w e r e t h e n w a s h e d w i t h
d e i o n i z e d w a t e r a n d ionexchanged inlMNH,NO,.
A l l t h e z e o l i t e e x h i b i t e d g o o d c r y s t a l l i n i t y a s w a s p r o v e d b y X-
r a y d i f f r a c t i o n a n d t h e i r d e s o r p t i o n c a p a c i t i e s . The I . R . s p e c t r a of
s k e l e t a l v i b r a t i o n s , OH-groups a n d p y r i d i n e a d s o r p t i o n w e r e r u n o n a
Specord 1 . R . - 7 5 spectrophotometer u s i n g s e l f - s u p p o r t i n g z e o l i t e
p l a t e s . The s p e c t r a d e p i c t e d c o r r e s p o n d e d t o a sample t h i c k n e s s of 3
mg/cm2. The samples were evacuated t o about lo-‘ Pa a t 7 2 3 K , p r i o r t o
measuring t h e s p e c t r a . The “ S i and 27Al s p e c t r a w e r e r e c o r d e d on a
Brucker CXR-200 s p e c t r o m e t e r w i t h t h e magic a n g l e s p i n n i n g . A 1 ( H 2 0 ) 2 *
c o m p l e x w a s u s e d a s a n internalstandardandsamplesweremeasuredin
theirhydratedstate.Atemperature-programmedsurfacemethod (TPSR)
( r e f . 5)wasusedtoinvestigatethebehaviourofmethanolpreadsorbed
onzeolites.
565
To i d e n t i f y t h e p r o d u c t s formedduringtheexperiment, t h e m a s s
range10-70m/ewasexaminedat15Kintervals. D e s o r p t i o n w a s c a r r i e d
outinvacuosothatthedesorbingspecies c o u l d b e d i r e c t l y o b s e r v e d
u s i n g a m o d i f i e d m a s s spectrometerM1-201. Methanolwas p u r i f i e d by
r e p e a t e d l y f r e e z i n g and pumping. Methanol vapour a d s o r b e d a t room
temperature.
RESULTBANDDISCUSSION
Structure
T h e Z e o l i t e p r e p a r e d w i th . S i C l , , h a d a f r a r n e w o r k S i / A l r a n g i n g from
4.3 t 0 4 2 . Itwasarguedthatmid-infrared s p e c t r o s c o p y m i g h t y i e l d
CM"
F i g . 1. Mid. i . r . spectraofnormalHYanddealuminatedsamples:
1. HY-(2.5) ; 2 . DY-(4.3); 3. DY-(4.8); 4 . DY-(7.3) ; 5. D Y - ( 4 2 ) .
informationabouttheframeworkchangesduringthedealuminationpro-
cess. The infraredspectraofdealuminatedYarecompared i n F i g . 1.
F r o m t h e s p e c t r a it i s e v i d e n t t h a t a l l t h e f r a m e w o r k v i b r a t i o n a l
.
modes a r e s h i f t e d upon d e a l u m i n a t i o n (&V= a b o u t 50 cm-‘) when t h e S i / A 1
r a t i o is i n c r e a s e d t h e medium bands a t 682 and 6 7 0 cm-’ a p p e a r . N o v i -
s i b l e d e s t r u c t i o n o f t h e frameworkduetodealumination isobserved.
Dealumination w i t h S i C 1 4 l e a d s t o t h e f o r m a t i o n o f non-framework
aluminium s p e c i e s i n t h e z e o l i t e p o r e s . T h i s is shown by t h e “ S i and
2 7 A l m.a.s.n.m.r. s p e c t r a of t h i s m a t e r i a l (see F i g s . 2 A , B ) . The A 1
m.a.s.n.m.r. spectrashowtwodistinctkindsofsignals- s h a r p p e a k s
( a t 5 6 ppm) d u e t o t e t r a h e d r a l l y c o o r d i n a t e d A 1 i n t h e z e o l i t e frame-
OH-UrOUDS
I . R . spectra intheOH-stretchingregionofy zeolites,dehydrated
a n d d e a m m o n i a t e d a t 7 2 3 K, are r e p r e s e n t e d i n F i g . 3A.
\
3700 3500 CM-~ 1700 1500
A B
F i g . 3. I . R . s p e c t r a i n t h e regionoftheOH-stretchingnumber ( A ) :
t o ( - ) a n d a f t e r (---) p y r i d i n e a d s o r p t i o n (B) O f n o r m a l H Y a n d d e a l u -
minated samples: 1. HY-(2.5) : 2 . DY-(4.3) : 3. DY-(4.8) : 4 . DY-(7.3) :
5. D Y - ( 4 2 ) .
I n c l o s e a g r e e m e n t w i t h t h e l i t e r a t u r e c o n c e r n i n g H f o r m s o f zeo-
l i t e s o b t a i n e d through NH; exchange, I . R . bands are observed a t 3640
and 3540 cm-‘, a t t r i b u t e d t o t h e hydroxyl i n t h e l a r g e and s m a l l c a g e s ,
c o r r e s p o n d i n g l y . DifferencesintheI.R.spectraofhydroxyldea1umi-
natedwithSiCl4productsprovidedevidenceoftheessentialinfluence
ofthemodificationprocedure onthepropertiesofthesegroups.
The band a t 3 6 4 0 cm-’ s h i f t e d t o c a . 3630 cm-‘ f o r S i / A 1 = 4 . 8 and t o c a .
3 6 2 0 cm-’ f o r S i / A l > 4 . 8 . The i n t e n s i t y of t h e I . R . band changed w i t h
increasingSi/Alratio.Newunspecifiedhydroxylvibrationsappeared
a t 3610 cm-’ and 3510 cm*’. Slow d e c r e a s e of i n t e n s i t y of t h e I . R .
bands accompanied by t h e appearance and r a p i d i n c r e a s e o f a band a t
3 7 2 0 cm-’ w e r e observed.
T h e n a t u r e o f t h e a c i d s i t e s a n d t h e i r r e l a t i v e strengthswere
s t u d i e d by means of i n f r a r e d s p e c t r a f o l l o w i n g p y r i d i n e a d s o r p t i o n .
Pyridinewasadsorbedandthenevacuatedat423 K.Thebandsduetothe
c h e m i s o r b e d p y r i d i n e a r e shown i n F i g . 3 . U n e x p e c t e d r e s u l t s f o r a l l
dealuminated samples were o b t a i n e d . I n c o n t r a s t w i t h t h e l i t e r a t u r e
d a t a f o r H forms of f a u j a s i t e - l i k e z e o l i t e s , a d s o r p t i o n of P y r i d i n e
c a u s e s a s h a r p d e c r e a s e i n t h e i n t e n s i t y of t h e OH-bands a t 3 5 4 0 cm-’.
Simultaneously, a s s e e n i n t h e s p e c t r a , bands a t t r i b u t e d t o t h e C-C
s t r e t c h i n g v i b r a t i o n o f t h e p y r i d i n i u m i o n (1550 cm-’) a n d c o o r d i n a t i v e
bonded p y r i d i n e complex ( 1 4 5 0 cm-’) were observed. Besides, thermal
s t a b i l i t y t h e s e complexes i n c r e a s e w i t h i n c r e a s i n g S i / A 1 r a t i o .
According t o Belanski thermal s t a b i l i t y can be used a s a measure o f t h e
acidstrengthof zeolites.
Moreover,basicstrengthhasbeenstudiedinzeolitesdealuminated
w i t h S i C 1 , by u s i n g p y r r o l e a d s o r p t i o n . A s h i f t i n t h e NH s t r e t c h i n g
bandofadsorbedpyrroleandthepresenceo€comb~nat~onbandsat2940
and 2850 cm-’ were observed ( r e f . 6 ) .
TPSRofmethanol
Inordertomoreclearlyunderstandthepropertiesofthedealu-
minatedYzeolitesweinvestigatedthetemperature-progra~edsurface
r e a c t i o n of methanol preadsorbed a t ambient t e m p e r a t u r e . The TPSR
spectrafortheproductsofthemethanol-zeoliteinteractionareshown
i n Fig. 4A.
569
A B C
+
x 5
-7
n o l d o e s n o t evacuate e a s i l y i n a n u l t r a h i g h v a c u u m , w e b e l i e v e t h a t
theseolefinsareformedbythereactionbackgroundgasespassingover
thezeoliteathightemperaturesduringTPSR.~sit~infraredspectra
of t h e methanol dealuminated samples r e i n f o r c e t h i s c o n c l u s i o n
( r e f .7).
Thus, f r o m t h e a b o v e r e s u l t s , itcanbeconcludedthatinthecaseof
S i C l , t r e a t m e n t , h i g h c r y s t a l l i n e p r o d u c t s are o b t a i n e d w i t h u n u s u a l
distributionsofLewisandBronstedacidityandwithanticipatedcata-
l y t i c p r o p e r t i e s . I.R. and m.a.s.n.m.r. d a t a demonstrated t h a t t h e
chemical p r o p e r t i e s of A 1 i n t h e z e o l i t e l a t t i c e are n o t homogenous
and c h a r a c t e r i z e ( v a r i o u s ) t y p e s of aluminium sites. I n agreement w i t h
Kubelkova e t a l . ( r e f . 8 ) , it seems r e a s o n a b l e t o assume t h a t t h e
cationicaluminiumspeciesgenerallyprovidetheAlelectronaccepting
centers.Thequestionremainsoftheoverlookedfactoftheinteraction
of p y r i d i n e w i t h low f r e q u e n c e h y d r o x y l s a t 3 5 4 0 cm-’. I t seems t o be
i m p o s s i b l e , when t a k i n g i n t o account t h e p e c u l i a r s t r u c t u r e o f t h e
f a u ja s i t e .
Ontheotherhand,itisevident,thatextra-framework-typealumina
affectthepropertiesofYzeolites.Thedea1uminationprocessenhan-
cedtheacidityofthe zeolitesbutthismay occureitherviathenon-
frameworkspeciesorbygeneratinga z e o l i t e i n w h i c h m o s t o f t h e a l u -
minahavenonearestneighborsalumina. I t i s a l s o c o n s i s t e n t w i t h t h e
conceptofapreferredaluminiumdistributionsimilartotheDempsey
model.
Thebasicityofoxy-compoundscanalsobediscussed i n t e r m s o f t h e
dataobtained.ComparedwithnormalHY,dealuminatedzeolitesexhibit
anacido-basiccharacterandthusconsitutearelatedsystemwithnew
p r o p e r t i e s . I n summary, w e b e l i e v e t h a t t h e r e s u l t s p r e s e n t e d h e r e g i v e
a b e t t e r u n d e r s t a n d i n g o f t h e d u a l c h a r a c t e r of z e o l i t e s ( r e f . 9).
F u r t h e r s t u d i e s on t h e n a t u r e of a c i d o - b a s i c s i t e s and t h e c a t a l y t i c
propertiesofdealuminatedSiCl4Yzeolitesareinprogress.
AC KNOW LEDOMENT
TheauthorsexpresstheirappreciationtoDr.V.V. B r e i ( I n s t i t u t e
ofSurfaceChemistryUkrainianAcademyofSciences,Kiev)f o r h i s k i n d
presentationofthem.a.s.n.m.r.data.
571
REFERENCES
1. J. S h e r z e r , Octane-enhancing, z e o l i t e F C C c a t a l y s t s : S c i e n t i f i c a n d
t e c h n i c a l a s p e c t s , Catal.Rev.Sci.Eng., 31(3) (1989) 215-354.
2. E. Dempsey, Acid S t r e n g t h and aluminium s i t e r e a c t i v i t y o f Y zeo-
l i t e s , J . C a t a l . , 33(3) (1974) 497-499.
3. B. Beagly, J. Dwyer, F.R. F i t c h , R. M a n n a n d J . Walters, Aluminium
d i s t r i b u t i o n and p r o p e r t i e s o f f a u j a s i t e s . B a s i s of models and
z e o l i t e a c i d i t y , J . Phys.Chem., 88(4) (1984) 1744-1751.
4. I . V . Mishin, G.K. Beyer, A.L. Klyachko, G.A. Ashavskaja, V.D.
Nissenbaum and G. Borbely, R e c e i p t of h i g h s i l i c a f a u j a s i t e w i t h
S i c l , , Kin. i k a t . , 28(3) (1987) 706-711.
5. A . I . P r i l i p k o . G.M. T e l b i z , V.G. I l i n , V.P. Shabelnikov, E.N. Korol,
Somepeculiaritiesofdesorptionofthe z e o l i t e i n t h e T P S R c o n d i -
t i o n , Dokl. ANUkr. SSR, s e r B , 3 (1989) 55-57.
6. G.M. T e l b i z , A.V. S v e t z , s u b m i t t e d f o r p u b l i c a t i o n .
7. G.M. T e l b i z , V . V . B r e i , i n p r e p a r a t i o n .
8. L. Kubelkova,S. Beran, A . M a l e c k a , . V . M a s t i k h i n , A c i d i t y o f m o d i -
fiedzeolite.EffectofnonskeletalAlformedbyhydrothe~a1treat-
ment, d e a l u m i n a t i o n w i t h SiC1, and c a t i o n exchange w i t h A l l Zeo-
l i t e s , 9(1) (1989) 12-17.
9. D. Bartomeuf, C o n j u g a t e a c i d - b a s e p a i r s i n z e o l i t e s , J. Phys.Chem. ,
88(1) (1984) 42-45.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 573
0 1991 Elsevier Science PublishersB.V., Amsterdam
ABSTRACT
The formation of zeolite ZSM-5 is studied from five different
gels having various A1 content. The crystallization kinetics, the
nucleation kinetics, the pH of mother 1 iqiiors, the physical state
and the composition of the solid phases are examined by combined
physico-chemical techniques: SEM, X-ray Diffraction, Atomic Absor-
ption, Elemental analysis and Thermal Analysis (TG, DTG, DTA).
INTRODUCTION
Zeolite ZSM-5 (see ref. 1) is widespread in the petrochemical
industry as a catalyst for various processes. Because of its note-
worthy properties this zeolite has been widely investigated, and
the numerous information gathered makes ZSM-5 a good model to
test current theories on zeolite nucleation (see refs. 2,3) and
growth (see refs. 4-12). The object of the present work is to cha-
racterize the products and derive nucleation kinetic curves of
Na,TPA-ZSM-5 zeolite in five systems differing by the aluminium
content in the starting gel. The products are characterized in
different ways: the pH of the mother liquors is measured, and the
sol id phases during the crystal 1 ization are analyzed and examined
by TGA and chemical analysis methods.
EXPERIMENTAL
Zeolites ZSM-5 were synthesized hydrothermally in static condi-
tions at 170f2'C under autogenous pressure from systems having mo-
lar ratios 5Na,0-8.8(TPA),0-xA1,03-100Si02-1250H20, with x=O. 125,
0.177,0.289, 0.626, 0.987,for runs A, B, C , D and E, respective-
ly. Reagents were carefully admixed in the order: Al(OII), gel dry
(Serva 'reinst' grade) with composition AI,OR.4.6iOFI,O (TBA.
574
11.5
11.1
10.7 ' I I I 1
1'0
I I I I
210
I I I
t/h
I I I I I I
-~i-o-Si- + 0118 2 -Si-OII + 'O-Si- 7 -si-o-si- + OH^
I I I I I I
(amorph .) (aq. 1 (aq. 1 (cryst.)
TABLE 1
C o m p o s i t i o n of t h e s o l i d p h a s e s : runs C and D
Run C Run D
amorph. crystals amorph. crystals
t/hNa% 8 Naa Ala
A1
TPAa'b Na% 3 Naa Ala
A1
TPAajb
z (t)
1.0
0.5
0
0 5 10 15 20 25
t/h
TABLE 2
Linear growth rate of crystals and maximum nucleation time
A B C D E
40
ik
0
IC
30
20
10
I
0 5 10 15
t/h
DISCUSSION
Previous studies (see ref. 8) showed that the conversion rate
and the yield of silicalitc-1 arc favored by the amount of TPA
ions up t,o TPA/Si m o l a r ratio equal to 0.08. Hence, an excess of
‘ W A beyond that, v a l u e i s not influent, any more on these parame-
ters. The amount of organic ion in our samples (TPA/Si=0.088) is
t h e r e f o r e optimal and does not. c n n R t , i t r i t . e PL 1 i m i t . i n r f f n * o * n r
579
ACKNOWLEDGEMENTS
We gratefully acknowledge D r . Nicola La Rosa for kindly supply-
ing calculation facilities. This work h a s been supported by CNR
(Italian National Rcsearch Council), Progetto Finalizzato Chimica
Fine e Sccondaria.
REFERENCES
1 R.J. Argauer and G.R. Landolt, U . S . Pat. 3,702,886.
2 J.C. Jansen, C.W.R. Engelen and 11. van Rekkum, ACS Symp. Ser.,
398 (1989) 257.-68
3 B. Subotib, ACS Symp. Ser., 398 (1989) 110-21.
4 R . A . Van Santen, J. Keijsper, G . Ooms and A.G.T.G. Kortbcek,
Stud. Surf. Sci. Catal., 26 (1986) 169-75.
5 D.C. Hayhusrt, R. Aiello, J. B.Nagy, F. Crea, G . Giordano, A .
Nastro and J .C. Lee, ACS Symp. Ser., 368 (1988) 277-91.
6 G . Boxhoorn, 0. Sudmeijer and P . 1 I . G . van Kasteren, J. Chem.
SOC.,Chem. Commun., (1983) 1416-8.
7 J. B.Nagy, P. Bodart, E.G. Derouane and Z. Gabclica, Stud.
Surf. Sci. Catal., 26 (1986) 231-8.
8 F . Crea, A . Nastro, J. B.Nagy and R . Aiello, Zeolites, 8
(1988) 262-8.
9 R . Aiello, F. Crea, A. Nastro and C. Pellegrino, Zeolites, 7
(1987) 549-53.
10 A. Araya and B.M. Lowe, Zeolites, 6 (1986) 111-8.
11 B.M. Lowc, Stud. Surf. Sci. Catal., 37 (1987) 1-12.
12 G . Bellussi, G . Perego, A. Carati, U . Cornaro and V. Fattore,
Stud. Surf. Sci. Catal., 37 (1987) 37-44.
13 G. Golemmc, A. Nastro, J. B.Nagy, B. Subotik, F. Crca, and R .
Aiello, in preparation.
14 P.T. Cardew and R . J . Davey, Proc. R . SOC. London A, 398
(1985) 415-28.
15 Z. Gabelica, J. B.Nagy, P. Bodart, N. Dewaele and A. Nastro,
Zeolites, 7 (1987) 67-72.
16 S . P . Zhdanov and N.N. Samulcvich, in: L.V.C. Rees (Ed.), Proc.
5th Intl. Conf. on Zeolites, lleyden, London, 1980, p p . 75-84.
17 V.N. Romannikov, V.M. Mastikhin, S . HoEevar and B . Driaj,
Zeolites, 3 (1983) 311-20.
1 8 S . B . Kulkarn i , V.P. Shi ralkar, A.N. Kotasthane, R.B. Borade
and P . Ratnasamy, Zeolites, 2 (1982) 313-8.
19 K.-J. Chao, T.C. Tasi and M.-S. Chen, J. Chem. SOC., Faraday
Trans. I , 77 (1981) 547-55.
20 P. Bodart, J . B.Na y , 2. Gabalica and E;.G. Derouane, J. Chim.
Phys., 83 (11-12) fi986) 777-90.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 581
0 1991 Elsevier Science PublishersB.V., Amsterdam
SUMMARY
Vanadium silicalite KVS-5 has been grown under conditions of hydrothermal
synthesis. Its structure corresponds to the MFI type. The product can be syn-
thesized with a yield of 100% in form of slightly coloured large crystals up to
300 m. The incorporation of V5+ ions on T-sites in the zeolitic framework has
been investigated by a variety of methods: XRD, MAS M,SSIMS, ESR, TGIDTA.
IR. and XRF.
INTRODUCTION
The catalytic properties of vanadium compounds and especially of its oxides
have been investigated and used since the 1960's. These studies of vanadium ca-
talysts were dealing mainly with the changes of oxidation state of vanadium
during the catalytic process as well as with the role of support. Commonly. si-
lica or alumina [l-31 have been used as supports for the vanadium compounds. No
catalysts have been prepared with an exactly defined state of this metal except
for the synthesis of heteropolyacids [4].
An introduction of vanadium into the ZSM-5 zeolite crystals has been already
reported: Kucherov et al. 15-81 and later Sass et al. [9] introduced V4+ ions
into extra-framework cationic positions by a solid state reaction. Inui e l al.
[lo] introduced vanadium compounds instead of the A1 component already into the
reaction gel for synthesis of the zeolitic catalyst. The possibility of isomor-
phous substitution of a large number of elements with vanadium in three diffe-
rent oxidation states 111, IV, and V has been published by Xu Ruren et al.[ll].
Nevertheless, they have given neither synthesis conditions nor any proof or me-
thod for checking the actual incorporation of those elements into the crystal
structure except that they report lattice constants. The differences in these
lattice constants compared to ZSM-5 seem to be much too high considering the
amounts of heteroatoms which could be possibly incorporated into the framework.
582
The aim of this work was to prepare a crystalline porous zeolite with iso-
morphously substituted Vt5 ions in the framework as a precursor of a catalyst
for oxidation reactions and to check the product with a variety of methods
which could show real substitution.
EXPERIMENTAL
The zeolite was synthesized in teflon-lined autoclaves by reacting silica s o l ,
alkali metal vanadate, sodium bicarbonate, tetrapropylammonium hydroxide
(TPAOB) and water at 160-190.C and autogeneous pressure for 5-9 days followiiig
the procedures given in refs. [12.13]. Reference samples were prepared by im-
pregnation of silicalite with VOSO4 and by synthesis of VA1-ZSM-5 using analo-
gous methods to KVS-5. The impregnation procedure was the following: siljcalite
was stirred for 24 hs at RT and pH = 3 in an 0,1 M water solution of VOSO4 ( 2 0
ml/lg of zeolite), then washed with water, dried at 80'C for 3 hs and finally
calcined at 500.C for 1 h in air. Calcination of KVS-5 samples was made at
500'C for 48 hs in a slow air stream and 24 hs i n an 02 stream.
The products were characterized by XRD. SEM. MAS NMR, SSIMS, ESR, TG/DTA,
and IR techniques.
Apparatus used and condi.tionsof measurements:
XRD: DRON 3 with PC, CuKa radiation, 0,5'/min
SEM: NOVOSCAN 30. samples covered with Au
MAS NMR: BRUKER CXP 200 equipped with 4.8 T magnet
ESR: TSN-254 and SE/X 2544 Radiopan
TG/DTA: MOM Q-1500, heating rate 1O0C/min, sample 400 mg
IR: UR 20
SSIMS: LAS-3000 RIBER. range 0-200 amu. time 30 min.
la
lb
2a
2b
constants larger than the experimental error occurred after calcination which
suggests a relaxation of the framework after removal of the template molecules.
Thermogravimetry analysis (Fig. 3 ) shows that the calcination process pro-
ceeds with three thermal effects: endo- and exo-thermal effects at about 350 -
360'C overlapping one another and coinciding with a weight loss and the third
T
PC
800
DTG
-.----L -'\~
\ -
600
LOO
200
strong exothermal effect at -520.C not followed by a weight loss. The endo-ef-
fect. is connected with the template decomposition. Then the decomposition pro-
ducts leave the sample (weight loss) causing a relaxation of the framework
(exo-effect and decrease of lattice constants). The exo-effect at -520.C can be
due to combustion of the organic decomposition products outside the sample. The
last effect is not observed when the calcination proceeds in a stream of gas
(the decomposition products are taken away from the system). The possibility of
a two step mechanism of the template removal was already reported [14]. All
these effects are probably well resolved due to both the large dimensjons of
the crystals and the high amount of sample hindering diffusion processes.
The static SINS data (Fig. 4) show that KVS-5 samples are free from A1 and
F e impurities (confirmed in ESR spectra) and the vanadium content (lines 51 and
67 for V(+) and VO(+), respectively, and no 181 line for V*O5(+) [15]) can
586
72
LL
I
Fig. 4. Static
secondary ions
mass spectroscopy
data for
vanadium s i l i c a l i t e
KVS-5.
Fig. 5. Infrared
spectra of vanadium
s i l i c a l i t e KVS-5
before ( a ) and
a f t e r (b)
calcination.
l l . l l l . l l l l l
1500 1000 500 cm-'
587
3PPH
I __c
H
200 G
I-----+
DPPt
Fig. 7. ESR s p e c t r a of
a ) sample p r e p a r e d by
impregnat ion of sit i c a l i t e
w i t h VOSO4, b ) VAL-ZSM-5
a f t e r calcination.
I I I I I I
3,lO 330 35 0 37 0
H [kGl
After calcination, the vanadium ions represented by the hyperfine ESR spec-
trum are completely oxidized to V5+ and the ESR signal vanishes. The broad
lines in Figs. 6b and 7a remain unchanged after calcination showing that the
clustered V4+ is not oxidized. In the ESR spectrum of calcined VAl-ZSM-5. the
hyperfine structure is not vanishing completely (Fig. 7b) which might suggest a
hindering role of A1 in the oxidation of V4+.
The 51V MAS NMR spectrum of calcined KVS-5 shows the band at -557 ppm
(Fig. 8 ) corresponding to vanadium complexes with a tetrahedral oxygen envi-
ronment [ I , 181 which might indicate again the incorporation of vanadium into
the framework. Fig. 9 presents the spectrum for silicalite impregnated with
VOSO4 (measured immediately after calcination). As V4+ should not give any NMR
spectrum, the extremely broad band (Av 0 110 kHz) at about -620 ppm can be
identified as the band due to a small amount of V5+ ions broadened because of
the influence of V4+ present in excess. A similar band at about -530 ppm with a
small shoulder at --I000 ppm is observed for as-prepared KVS-5 except for a
narrower width -17,5 kHz probably due to a much lower content of vanadium.
As it appears from 27Al MAS NMR spectrum of as-prepared VAL-ZSM-5 (Fig.10).
5 - 20% of the Al3+ ions are in octahedral coordination ( s e e the band at -0
pprn). This band vanishes completely after calcination and only the band for
tetrahedral A 1 at +50 ppm remains, thus proving the tendency of A1 for entering
tetrahedral coordination during heat treatment [ 1 9 ] .
CONCLUSIONS
The results show the possibility of preparation of vanadium silicalite KVS-5
containing approximately 1% vanadium. The vanadium atoms in the as-prepared
material exist mainly as V4+ ions and after calcination they are oxidized to
V5+. In both cases, they are tetrahedrally coordinated and they occur in a
highly dispersed state. Depending on synthesis conditions, a part of the vana-
dium can occur as clustered extra-framework V4' species which are difficult to
oxidize. After calcination, the vanadium atoms in KVS-5 appear to be in a more
uniform state than before.
The work was partially supported by the Polish Ministry of National Education
within the Project CPBP 01.06.
REFERENCES
1 V.M. Mastikhin, K.l. Zamaraev. Z. Phys. Chem. Neue Folge, 152 (1987). 317.
2 B. Taouk, M. Guelton, J . Grimbolt. J.P. Bonnelle, J . Phys. Chem., 92
(1988). 6700.
3 K.J. Zhen, M.M. Khan, C.H. Mak, K.B. Lewis, G.A. Somorjai, J . Catal., 96
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7 A.V. Kucherov. A.A. Slinkin, Zeolites, L (1987). 43.
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10 T. Inui, A. Miyamoto. H. Matsuda, H. Nagata, Y. Makino, K. Fukuda. F.
Okazumi, Proc. 7th Int. Zeolite Corif.. Tokyo, 1986, Y. Murakami et al.
(Eds.). Kodansha, Tokyo, 1986. 859 and refs. 12-14 therein.
1 1 X u Ruren. Pang Wenqin, Proc. Tnt. Symp. Zeolites, Portoroz, 1985, B. Drzaj
et al. (Eds.), Elsevier, Amsterdam, 1985, Stud. Surf. Sci. Catal.. 24
(1985). 27.
1 2 J . Kornatowski, M. Rozwadowski, Pol. Pat. Appl., P 281513, (1989).
13 J . Kornatowski. Zeolites, 8_ (1988), 77.
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377.
15 C. A. Altomare, G.S. Koermer, E. Martins, P.F. Schubert, S.L. Suib, W.S.
Willis, Appl. Catal., 45 (1988). 291.
16 G . Perego, S. Bellussi, C. Corno, M. Taramasso, F. Buonorno, A. Esposito,
Proc. 7th Int. Zeolite Conf., Tokyo, 1986, Y. Murakami et al. (Eds.),
Kodansha, Tokyo, 1986, 859.
17 B. Kraushaar. J.H.C. van HooIf, Catal. Lett., L(1988). 81.
18 L.R. Le Coustumer. B. Taouk, M. Le Meur, E. Payen, M. Guelton. J. Grimblot,
J. Phys. Chem.. 92 (1988), 1230.
19 J. Kornatowski. M. Rozwadowski, W. Schmitz, A. Cichowlas, Proc. 8th Int.
Zeolite Conf., Amsterdam, 1989. Recent Research Reports Val., J.C. Jansen
et al. (Eds.). L.. Moscou, Akzo Chemicals, Amsterdam, 1989, 79.
G. Ohlmann et 01. (Editors),Catalysis and Adsorption by Zeolites 591
01991 Elsevier Science Publishers B.V., Amsterdam
ABSTRACT
A series of intermediate phases, isolated during the synthesis of
SAPO-37, have been characterized by XRD, SEM, NMR of adsorbed Xe, and
solid state 27Al- and 31P-NMR, in order to evidence the successive steps
occurring during the crystallization process. SAPO-37 stems from a
direct gel restructuration: large cavities form in the amorphous phase
during the aging period at ambient temperature. Upon heating at 200°C,
aluminum and phosphorus respectively incorporate in configurations
Al(4P) and P(4AI) in the framework, at the expense of the amorphous
phase, giving rise to the formation of well-defined SAPO-37 crystals,
showing an octahedral morphology, and growing with time. The
crystallinity reaches a maximum after 32h. For excessive synthesis times
(149h), the appearing of structural defects observed by NMR illustrates
the partial degradation of the SAPO-37 framework, whereas a side-phase,
SAPO-40, possibly involving interconnected channels limited by 12T
puckered rings, co-crystallizes from the mother liquid phase.
INTRODUCTION
The synthesis of SAPO-37, a silicoaluminophosphate involving a
Faujasite topology [ref. 11 was first reported by Lok et al. [ref. 21. Because
of its open pore structure, this material possesses potential interesting
and attractive applications in catalysis or adsorption, this explaining the
increasing attention that is now being devoted to the understanding of its
synthesis and to its better characterization. We have recently examined
the influence of various synthesis variables (aging time and temperature,
agitation and crystallization time) on the nature and final properties of
the various SAPO-type open structured phases obtained by two different
methods currently yielding SAPO-37 [ref. 31. Our study allowed us to
define the optimal conditions under which pure SAPO-37 could be obtained
in high yield by using both the conventional "aqueous" synthesis [ref. 21 or
592
the new biphasic (water-hexanol) route [ref. 41. The short range structural
configuration and coordination of Si, Al and P and their distribution in the
SAPO-37 framework, as well as the mechanisms governing the potential
framework substitution of Al or P by Si in the Faujasite structure, have
been thoroughly investigated by high resolution solid state NMR (29Si,
27AI, and 31P) [refs. 3, 5-71. The same techniques [ref. 81, complemented
by 129Xe-NMR [ref. 91 were used to follow the structural changes occurring
when water and organic template molecules progressively escape from the
SAPO-37 intracrystalline volume upon various thermal treatments.
Finally, we have recently taken advantage of the multiple potentialities of
the 129Xe-NMR method, linked to the great sensitivity of the xenon nucleus
to its close environment [refs. 10, 111 to characterize a series of
intermediate phases isolated during the hydrothermal synthesis of SAPO-
37 [ref. 121.
In the present work, we confirm and complete these preliminary
129Xe-NMR data by investigating more in depth the successive stages of
the crystallization (gel restructuration, crystal growth, formation of a
side-phase) and by characterizing all the solid intermediates using
complementary 27Al- and 31 P-NMR, in combination with XRD and SEM
techniques.
EXPERIMENTAL
The optimized procedure followed to synthesize the intermediate and
final SAPO-37 phases was described in details in our previous papers
[refs. 3, 121. Several aliquots of a hydrogel of molar composition 1.0
A1203 : 0.9 P2O5 : 0.4 Si02 : 0.86 (TPA)20 : 0.023 (TMA)20 : 50 H20,
previously aged at 20°C for 48h, were heated at 200°C under stirring
conditions for various periods of time. For the present study, we have
selected the more representative samples among the intermediates
isolated during the crystallization course. These specimens were obtained
after 0, 5, 10, 32 and 149h of heating, and are referred to as Pn, where n
denotes the crystallization time (Tablel).
The as-synthesized materials were checked for nature and purity by
X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).
The percentage of SAPO-37 in each phase was estimated by comparing the
total surface area of the characteristic XRD peaks measured for this
sample to the area of the same peaks recorded for the most crystalline
SAPO-37 of the series, arbitrarily considered 100% crystalline (P32)
(Tablel). The xenon adsorption isotherms were measured at 34% using a
classical volumetric apparatus, following operating conditions described
593
TABLE 1
Nature, relative xenon adsorption capacities and relative crystallinities of
the intermediate phases isolated during the crystallization course of
;APO-3;
27Al and 3ps ( d 2 ) and 30s for 31P, respectively. Typical measuring
conditions for the 31P- CP-MAS NMR experiments were a 1H pulse length of
2.5ps, a contact time of l m s and a recycle time of 5s.
Fig. 1. SEM micrographs of the various intermediate phases. (a) Po, (b) P5, (c) Pio,
(4 P25, (el P32, (f) PIN.
100 0 -100
PPM
100 0 -100
PPM
I . . . . I . . . . I . . . . I ..
0 -50
PPM
I
-25
I
' I
-35
PPM Fig. 5. 31P-NMR spectra of the as-
Fig. 6. Simulation of the 31P-NMR synthesized intermediate phases.
spectrum of as-synthesized phase (a) Po, (b) P5, ( 4 Pie, (4 P25, ( 4
p25. p32, ( f ) p149.
600
CONCLUSION
129Xe-, 27Al- and 31 P-NMR techniques, combined with XRD and SEM,
have been proved a useful tool to investigate the successive steps
occurring during the crystallization process of SAPO-37. 129Xe-NM R was
of particular interest to detect the presence, at the early stages of the
crystallization, of preliminary void structures in the gel, which are not
observable by XRD or SEM. It allowed to follow to progressive increase of
the crystallinity of SAPO-37 and to evidence the partial degradation of its
framework, as well as the formation of the side-phase SAPO-40, upon too
long hydrothermal crystallization. The progressive incorporation of
phosphorus and aluminum into tetrahedral positions in the SAPO-37
network, at the expense of the phosphorus and penta-coordinated aluminum
belonging to the amorphous phase, was well illustrated by the 31P- and
27AI-NMR spectra of the successive intermediate phases. 27AI- and 31 P -
NMR also allowed to evidence the formation of structural P(OH), and
AI(0H)n defects in SAPO-37, and the appearing of SAPO-40 after a long
period of heating at 200°C, as well as the interactions of some framework
Al and P atoms with occluded organic molecules.
REFERENCES
B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan and E.M.
Flanigen, J. Am. Chem. SOC., 106 (1984) 6092-6093.
B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan and E.M.
Flanigen, U.S. Patent 4, 440, 871 (1984).
L. Maistriau, N. Dumont, J. B.Nagy, 2. Gabelica and E.G. Derouane,
Zeolites, 10 (1990) 243-250.
E.G. Derouane and R. von Ballmoos, Eur. Patent 185, 525 (1986).
L.S. Saldarriaga, C. Saldarriaga and M.E. Davis, J. Am. Cham. SOC, 109
(1987) 2686-2691.
C.S. Blackwell and R.L. Patton, J. Phys. Chem., 92 (1988) 3965-3970.
J.A. Martens, C. Janssens, P.J. Grobet, H.K. Beyer and P.A. Jacobs, Stud.
Surf. Sci. Catal., 49A (1989) 215-225.
M. Goepper, F. Guth, L. Delmotte, J.L. Guth and H. Kessler, Stud. Surf.
602
SUMMARY
T h e i n f l u e n c e of o r g a n i c c o n c e n t r a t i o n , S i / A 1 r a t i o , s t i r r i n g
and n a t u r e o f t h e s i l i c a s o u r c e on z e o l i t e s y n t h e s i s i n t h e
p r e s e n c e o f t e t r a e t h y l a m m o n i u m h a v e b e e n s t u d i e d . Examples o f
m e t a s t a b i l i t y o f z e o l i t e b e t a a n d ZSM-5 t o w a r d s ZSM-12 p r o p o s e t h e
l a s t a s t h e more s t a b l e z e o l i t i c p h a s e i n t e t r a e t h y l a m m o n i u m m e d i a
f e a t u r i n g h i g h e s t Si/A1 r a t i o . E v i d e n c e s of h e t e r o g e n e o u s
n u c l e a t i o n o f z e o l i t e s o v e r amo r p h o u s o r c r y s t a l l i n e p h a s e s a r e
discussed.
1NT RODUCT I ON
Many s t u d i e s h a v e d e a l t w i t h z e o l i t e s y n t h e s i s i n t h e p r e s e n c e
o f t e t r a e t h y l a m m o n i u m , s i n c e t h e f i r s t r e p o r t of t h e s y n t h e s i s o f
z e o l i t e b e t a ( r e f . 1 ) . Recent p a p e r s have been e s p e c i a l l y d e v o t e d
t o t h e s y n t h e s i s o f z e o l i t e b e t a ( r e f s . 2 , 3 ) and t o t h e
c o m p e t i t i v e f o r m a t i o n o f z e o l i t e b e t a a nd ZSM-PO ( r e f s . 4 , 5). T h e
open l i t e r a t u r e p r e p a r a t i o n s o f t h e s e z e o l i t e s a r e a l w a y s b a s e d on
te t r a a l k y l o r t h o s i l i c a t e s , w h i l e p a t e n t s y n t h e s e s p r o p o s e i n o r g a n i c
s o u r c e s o f s i l i c a b o t h i n t h e case o f z e o l i t e b e t a ( r e f s . 1, 6 )
and i n t h e case of ZSM-12 ( r e f . 7 ) . The c r y s t a l l i z a t i o n
s e l e c t i v i t y i n t e t r a e t h y l a m m o n i u m m e d i a when c o m m e r c i a l i n o r g a n i c
s o u r c e s of s i l i c a a r e u s e d appears h en c e a s a p r o m i s i n g f i e l d of
investigation.
T h e n a t u r e of t h e s o u r c e of s i l i c a i n f l u e n c e s t h e
c r y s t a l l i z a t i o n i n a m u l t i p l e way. Beyond t h e d i f f e r e n t d e g r e e o f
polymerization of t h e s i l i c i c species i n s o l u t i o n , t h e s u r f a c e
p r o p e r t i e s o f t h e a m o r p h o u s s o l i d p r e s e n t i n t h e s y n t h e s i s medium
are deeply a f f e c t e d . A s a consequence, heterogeneous n u c l e a t i o n of
d i f f e r e n t p h a s e s can o c c u r and modify t h e s e l e c t i v i t y of t h e
p r e p a r a t i o n . E v i d e n c e s of p r e f e r e n t i a l n u c l e a t i o n of z e o l i t e s o v e r
604
METHODS
C r y s t a l l i z a t i o n e x p e r i m e n t s h a v e b e e n c a r r i e d o u t u s i n g two
t y p e s o f e x p e r i m e n t a l d e v i c e s : 120 a1 s t a i n l e s s s t e e l a u t o c l a v e s
f o r e x p e r i m e n t s i n s t a t i c c o n d i t i o n s and a 0.5 l i t r e s s t a i n l e s s
s t e e l r e a c t o r f o r experiments under s t i r r i n g . T h i s l a s t autoclave
wad e q u i p p e d w i t h a n a n c h o r - s h a p e d s t i r r e r and a sampling o u t l e t
a l l o w i n g specimens t o be withdrawn w i t h o u t a l t e r i n g t h e s y n t h e s i s
c o n d i t i o n s . The s y s t e m w a s d e s i g n e d s o a s t o a v o i d a c c u m u l a t i o n of
material i n s i d e s a m p l i n g p i p e and v a l v e s i n t h e c o u r s e of t h e
r e a c t i o n ( r e f . 1 5 ) . The r e a c t o r was h e a t e d b y a n e l e c t r i c a l
f u r n a c e r e g u l a t e d t h r o u g h a t h e r m o c o u p l e immersed i n t h e r e a c t i o n
m e d i u m . T h e h e a t i n g r a t e was 3 "C/min a n d t h e s t i r r i n g r a t e 150
rpm. S a m p l e s o f 1 U m l w e r e p e r i o d i c a l l y w i t h d r a w n f r o m t h e
a u t o c l a v e . T h e s o l i d f r a c t i o n was r e c o v e r e d b y f i l t r a t i o n . The
::lcar s o l u t i o n , c o n t a i n i n g t h e d i l u t e d m o t h e r l i q u o r , was
p r e s e r v e d f o r e l e m e n t a l a n a l y s i s . The s o l i d w a s washed w i t h
d e i o n i z e d w a t e r up t o p H Y a n d d r i e d a t 70 "C i n a i r . The
temperature of a l l syntheses, both s t i r r e d and i n s t a t i c
c o n d i t i o n s , was 1 5 0 ° C .
T h e r e a g e n t s w e r e s i l i c a s o l ( C e c a s o l 3 0 , S i O z 2 5 % , Na 0 . 2 % , A 1
6 0 ppm, pH 8 . 8 , g r a i n s i z e 1 2 - 1 8 n m ) , p r e c i p i t a t e d s i l i c a ( Z e o s i l
175MP f r o m Rhane P o u l e n c , Na U . Y % , A 1 0.4%, Hz0 6 . 5 % , grain s i z e
2-2U u , p o r e volume 0 . 0 8 m l / g ) . s o d i u m a l u m i n a t e ( C a r l o E r b a R L E ) ,
t e t r a e t h y l a m m o n i u m (TEA! h y d r o x i d e s o l u t i o n ( A l d r i c h ) , sodium
h y d r o x i d e ( P r o l a b o KP N o r m a p u r ) , d e i o n i z e d w a t e r . T h e r e a g e n t s
were m i x e d u n d e r s t i r r i n g i n t h e o r d e r : a l k a l i n e s o l u t i o n , o r g a n i c
a g e n t , a l u m i n a t e , s i l i c a . T h e m i x t u r e was s t i r r e d f o r 4 h r s a t
roam t empe r a t u r e b e f o r e t he b e g i n n i n g o f t h e s y n t lies i s .
X - r a y p o w d e r d i f f r a c t i o n ( C t i R T h e t a 60 d i f f r a c t o m e t e r , C u K a
r a d i a t i o n ) was u s e d t o i d e n t i f y t h e p h a s e s p r e s e n t i n t h e s o l i d
f r a c t i . o n . C r y s t a l s i z e and h a b i t were d e t e r m i n e d b y s c a n n i n g
e l e c t r o n m i c r o s c o p y ( C a m b r i d g e S l 0 0 i n s t r u m e n t , r e s o l v i n g power 7
nm).
605
RESULTS A N D DISCUSSION
C.om0p e t i Lian...be-ttwaen. an al.c.ine_,_. mx.deni..f_e.and..ze~l,i.t a .bet a
S y n t h e s i s b a t c h e s o f s t o i c h i o m e t r y 8.10[xNa-(l-x)TEA]~Alz03~
l Y . O S i 0 2 . 6 3 0 H z O (OH-/SiOz 0.72), w h e r e x s p a n n e d f r o m 0 t o 1, h a v e
b e e n h e a t e d a t 150°C f o r 72 h o u r s i n s t a t i c c o n d i t i o n s .
P r e c i p i t a t e d s i l i c a was u s e d a s s i l i c a s o u r c e . T h e p h a s e s f o r m e d ,
t h e e l e m e n t a l composition o f t h e p r o d u c t and t h e y i e l d s of s i l i c o n
and aluminum t h r o u g h o u t t h e p r e p a r a t i o n a r e r e p o r t e d i n t a b l e 1.
As t e t r a e t h y l a m m o n i u m c o n c e n t r a t i o n i n c r e a s e s t h e main p h a s e
formed p a s s e s from a n a l c i m e t o z e o l i t e b e t a t h r o u g h m o r d e n i t e . The
r o l e of t h e tetraethylammonium c a t i o n i n t h e formation of s i l i c a -
r i c h l o w - d e n s i t y c r y s t a l l i n e p h a s e s is e v i d e n t . From t a b l e 1 i t
emerges t h a t t h e aluminum i n c o r p o r a t i o n p r e s e n t s a minimum f o r
i n t e r m e d i a t e v a l u e s o f t h e t e t r a e t h y l a m m o n i u m c o n c e n t r a t i o n . The
phenomenon seems t o b e c o n s i s t e n t w i t h t h e f o r m a t i o n of m o r d e n i t e
more s i l i c i c t h a n t h e c o r r e s p o n d i n g z e o l i t e b e t a .
T h e m o r p h o l o g y o f some p r o d u c t s a r e d e p i c t e d i n f i g u r e 1. A t a
TEA/SiOz r a t i o o f 0 . 5 0 ( f i g u r e l a ) r o u g h i r r e g u l a r g r a i n s o f
z e o l i t e b e t a u p t o 1 . 5 cc l a r g e a r e f o r m e d , t o g e t h e r w i t h t a b u l a r
c r y s t a l s of mordenite 12 CI l o n g . Some o f t h e g r a i n s o f z e o l i t e
b e t a a p p e a r t o h a v e grown a r o u n d t h e e d g e s o f t h e m o r d e n i t e
c r y s t a l s . Rare s p h e r e s o f a n a l c i m e ( n o t d e p i c t e d ) p r e s e n t a
d i a m e t e r up t o 7 u . A t a TEA/SiOz r a t i o o f 0 . 1 6 ( f i g u r e lb)
co-crystallization of m o r d e n i t e and a n a l c i m e can be o b s e r v e d .
A n a l c i m e c r y s t a l s a r e l a r g e r ( u p t o 16 u) a n d p r e s e n t t h e {211}
t r a p s z o h e d r o n h a b i t . When n o t e t r a e t h y l a m m o n i u m was p r e s e n t i n t h e
s y n t h e s i s m i x t u r e ( f i g u r e l c ) t h e p r o d u c t i s composed by 2 5 u
l a r g e a n a l c i m e t r a p e z o h e d r a . The c r y s t a l e d g e s a r e e t c h e d by
c o r r o s i o n l i n e s , s u g g e s t i n g t h a t t h e s y s t e m h a s grown
u n d e r s a t u r a t e d f o r a n a l c i m e . Analcime is s p r e a d of 2 CI large
TABLE 1
Phase composition, e l e m e n t a l composition and material b a l a n c e a s a
f u n c t i o n a f t h e tetraethvlaamonium c o n t e n t af-the s y n t h e s i s b a t c h .
F i g . 1. S y n t h e s e s a t d i . f f e r e n t t e t r a e t h y l a m m o n i u m c o n c e n t r a t i o n .
F r o m t o p t o b o t t o m : TEA/Si02 0 . 5 0 ( a ) , 0 . 1 6 ( b ) a n d 0 . 0 0 ( c ) .
607
-\
\
0.038
Q, 0.020
-a 0.002
100
t (h) 200
F i g . 2 . N u c l e a t i o n l a g s o f z e o l i t e b e t a ( 0 ) a n d ZSH-12 ( 0 ) a s
f u n c t i o n s o f t h e m o l e f r a c t i o n of a l u m i n u m .
f l a k e s o f g i s m o n d i n e , d e t e c t a b l e i n t r a c e amount f r o m t h e p o w d e r
X-ray d i f f r a c t i o n s p e c t r a .
F ~ o u .~ e ~ l i tb.afa.t~-..Z.~n--_l.Z
e
Mixtures of s t o i c h i o m e t r y 0.08Na~0.30TEA-(x/2)Al~O~~(l-x)SiO~~
16Hz0 (OH-/SiOz 0.35) w i t h x r a n g i n g f r o m 0.038 t o 0 . 0 0 2 h a v e b e e n
h e a t e d a t 150°C i n a s t i r r e d r e a c t o r . S i l i c a s o l w a s t h e s o u r c e of
s i l i c a . T h e i n d u c t i o n lags p r e c e d i n g t h e d e t e c t i o n of t h e
c r y s t a l l i n e phases are r e p o r t e d i n f i g u r e 2. I n moderately s i l i c i c
s y s t e m s ( S i / A l 2 5 - 5 0 ) z e o l i t e b e t a f o r m s b e f o r e ZSM-1%. T h e
n u c l e a t i o n l a g o f ZSH-12 d e c r e a s e s when S i / A 1 i n c r e a s e s a n d a t
h i g h e r S i / A 1 r a t i o ( 5 0 0 ) ZSM-12 i s t h e f i r s t and u n i q u e
c r y s t a l l i n e p h a s e f o r m e d . Aluminum seems n e e d e d t o f o r m t h e
l a d d e r s o f 4-membered r i n g s t y p i c a l o f z e o l i t e b e t a ( r e f s . 16,
17), a l r e a d y p r o p o s e d a s a l u m i n u m l o c a t i o n ( r e f . 18). On t h e o t h e r
hand, t h e p r e s e n c e of s i l i c o a l u m i n a t e s p e c i e s a p p e a r s t o i n h i b i t
tlie f o r m a t i o n of t h e c r i s t o b a l i t e - l i k e w a l l s of i n t e r c o n n e c t e d
6-membered r i n g s t y p i c a l o f ZSM-12 ( r e f . 19).
O n t h e o t h e r hand a l u m i n u m a l s o m o d i f i e s t h e p h y s i c s o f t h e
s y s t e m . I f t h e amount o f s o l i d f r a c t i o n r e c o v e r e d f r o m
i n t e r m e d i a t e s a m p l i n g is c o n s i d e r e d , m a i n d i f f e r e n c e s a r e f o u n d a s
a f u n c t i o n of composition. I n t h e more a l u m i n i c s y s t e m a n
amorphous s o l i d is p r e s e n t t h r o u g h o u t t h e h y d r o t h e r m a l t r e a t m e n t .
I n t h e c a s e o f t h e more s i l i c i c s t o i c h i o m e t r y t h e s y s t e m i n i t i a l l y
c o n s i s t s o f a c l e a r s o l u t i o n . G e l l i n g , and r e c o v e r y of a n y s o l i d
f r a c t i o n from s a m p l i n g , b e g i n o n l y a f t e r one d a y a t t h e s y n t h e s i s
t e m p e r a t u r e . Anyway a n a m o r p h o u s s o l i d i s a l w a y s p r e s e n t when
zeolite nucleates.
608
C ~ m p e tf;iQo...he.tween
i z.e.Q.l.i.t.e..hzta...an.d._ZS.M.-...5
T h e n a t u r e o f t h e s o u r c e o f s i l i c a may i n f l u e n c e t h e p h a s e
s e l e c t i v i t y o f t h e s y n t h e s i s . Two g e l s o f s t o i c h i o m e t r y
(O
1.2Na20.9.2TEA~0~A120~~78SiOz~128O HH
zO-/Si02 0.24) h a v e b e e n
p r e p a r e d f r o m p r e c i p i t a t e d s i l i c a o r s i l i c a s o l . Under
hydrothermal treatment i n a non-stirred a u t o c l a v e t h e experiment
with p r e c i p i t a t e d silica has given o r i g i n t o z e o l i t e b e t a . In t h e
e x p e r i m e n t w i t h s i l i c a s o l u n d e r t h e same h y d r o t h e r m a l c o n d i t i o n s
ZSH-5 h a s b e e n f o r m e d .
T h i s s e l e c t i v i t y e f f e c t h a s n o t b e e n o b s e r v e d when t h e
s y n t h e s i s h a s b e e n c a r r i e d o u t u n d e r s t i r r i n g . Two g e l s o f
stoichiometry 2.2Na~0-8.8TEA~0~A1~0~~51Si0~~
(OH-/Si02
1040Hz0
0.36) have been p r e p a r e d from p r e c i p i t a t e d s i l i c a or s i l i c a s o l .
Under h y d r o t h e r m a l t r e a t m e n t b o t h g e l s g a v e o r i g i n t o z e o l i t e
b e t a . The c r y s t a l l i z a t i o n from s i l i c a s o l f e a t u r e d a l o n g e r
i n d u c t i o n t i m e (22 h o u r s v e r s u s 15) a n d b i g g e r c r y s t a l s o f z e o l i t e
( 1 . 5 v e r s u s 0.8 p ) .
T h e n u c l e a t i o n o f z e o l i t e b e t a is h e n c e e a s i e r when t h e
s y n t h e s i s g e l is p r e p a r e d f r o m p r e c i p i t a t e d s i l i c a , b o t h i n
s t i r r e d a n d s t a t i c c o n d i t i o n s . On t h e c o n t r a r y , s t i r r i n g seems t o
h i n d e r t h e f o r m a t i o n o f ZSH-5. T h i s e f f e c t a p p e a r s i n agreement
w i t h t h e l o c a t i o n o f ZSH-5 e m b r y o s a t t h e e x t e r n a l s u r f a c e o f t h e
a m o r p h o u s g r a i n s ( r e f . 8), w h e r e s t i r r i n g may a f f e c t t h e e p i t a x i a l
cond i t i o n s .
F r ~ mZ.SMk5 t Q ZSM-12
I n t h e p r e v i o u s l y c i t e d e x p e r i m e n t o f s t o i c h i o m e t r y 1.2Na2O.
u r i n g s i l i c a s o l , ZSH-5 p r o v e d
Y . Z T E A 2 0 ~ A 1 ~ 0 s ~ 7 8 S i 0 2 ~ 1 2 8f0eHa~t O
u n s t a b l e on l o n g e r s y n t h e s i s t i m e . The p h a s e c o m p o s i t i o n o f t h e
s y s t e m is r e p r e s e n t e d i n t a b l e 2 a s a f u n c t i o n o f t h e s y n t h e s i s
t i m e . A f t e r t e n d a y s i n h y d r o t h e r m a l c o n d i t i o n s ZSH-12 n u c l e a t e s
a n d ZSM-5 b e g i n s t o d i s s o l v e . A f t e r t w e n t y d a y s ZSM-12 is t h e main
c r y s t a l l i n e p h a s e p r e s e n t . The e v o l u t i o n o f t h e s o l i d c o m p o s i t i o n
i s a l s o r e p o r t e d i n t a b l e 2 . The o r g a n i c c o n t e n t f e a t u r e s a
minimum i n c o r r e s p o n d e n c e w i t h t h e h i g h e r y i e l d o f ZSH-5.
The e l e c t r o n m i c r o g r a p h s o f t h e s o l i d a t d i f f e r e n t s y n t h e s i s t i m e s
a r e r e p o r t e d i n f i g u r e 3 . F i g u r e 3a r e p r e s e n t s t h e z e o l i t e f o r m e d
a f t e r 10 d a y s i n h y d r o t h e r m a l c o n d i t i o n s . T h e X-ray d i f f r a c t i o n
p a t t e r n o f t h i s s a m p l e i n d i c a t e s t h e p r e s e n c e o f t r a c e s of ZSM-12
besides well-crystallized ZSM-5. The s a m p l e c o n s i s t s o f 35 p long
c h a r a c t e r i s t i c e u h e d r a l c r y s t a l s o f ZSM-5.
609
TABLE 2
P h a s e c o m p o s i t i o n , e l e m e n t a l c o m p o s i t i o n and material b a l a n c e
d u r i n g the 4-~xma!i.ii~n.nf
_zSK:3xd-_zSHzL2,
time crisfa.lLi~fy--% m o l e f r a c t i o n Y-isI d
(days) L e l e m e n t / S i + A l L
E x t e n d e d t w i n n i n g i m p l i e s t h a t t h e l a t e r a l f a c e s of t h e p r i s m s
a r e e s s e n t i a l l y ( 1 0 0 ) f a c e s . T h e c r y s t a l s p r e s e n t a l s o some l e s s
common f e a t u r e s . T h e i r l a t e r a l f a c e s a r e s p r e a d o f r e c t a n g u l a r
e t c h i n g f i g u r e s , c l e a r l y showing t h a t t h e s y n t h e s i s system h a s
grown u n d e r s a t u r a t e d f o r ZSM-5. This e f f e c t should be accounted
f o r by t h e p r e s e n c e o f a l e s s s o l u b l e c r y s t a l l i n e p h a s e . I n d e e d a
d e n s e p o p u l a t i o n o f s u b m i c r o n p r i s m a t i c c r y s t a l s are embedded i n
t h e ( 1 0 0 ) f a c e s of ZSM-5. T h e smaller p r i s m s a p p e a r t o h a v e g r o w n
up f r o m t h e s u r f a c e p r e c i s e l y o r i e n t e d w i t h r e g a r d s t o t h e ZSM-5
l a t t i c e . T h e i r main a x i s l a y s i n t h e (010) p l a n e a n d f o r m s a 53”
angle w i t h the <loo>direction o f ZSM-5. Also t h e n o r m a l t o o n e
f a c e o f t h e smaller p r i s m s l a y s i n t h e ( 0 1 0 ) p l a n e o f ZSH-5.
I t c a n b e o b s e r v e d t h a t t h e o r i e n t a t i o n of t h e smaller c r y s t a l s
c o u l d c o r r e s p o n d t o 234-12 c r y s t a l s g r o w i n g i n t h e <loo> d i r e c t i o n
f r o m a ( 2 0 1 ) f a c e l a y i n g o n t h e ZSM-5 ( 1 0 0 ) f a c e . T h i s o r i e n t a t i o n
a c c e p t e d , t h e ZSM-12 < 0 1 0 > d i r e c t i o n s h o u l d c o r r e s p o n d t o t h e ZSM-
5 < 0 1 U > d i r e c t i o n . An e p i t a x i a l r e l a t i o n c a n b e f o u n d b e t w e e n t h e
b parameters: 5 . 0 and 1 9 . 9 A , r e s p e c t i v e l y . O r i e n t e d n u c l e a t i o n of
a z e o l i t e over a n o t h e r z e o l i t e f e a t u r i n g e p i t a x y i n only one
d i r e c t i o n h a s a l r e a d y b e e n o b s e r v e d , f o r i n s t a n c e i n t h e case o f
o f f r e t i t e a n d m a z z i t e ( r e f . 14).
F i g u r e 3b d e p i c t s t h e s o l i d f o r m e d a f t e r 1 5 d a y s o f s y n t h e s i s .
The s u r f a c e o f t h e ZSM-5 c r y s t a l s is d e e p l y e t c h e d a n d a h o p p e r
p i t i s open i n t h e ( 0 1 0 ) f a c e s . The s u r f a c e o f t h e l e s s - e r o d e d
c r y s t a l s is s p r e a d o f s l i g h t l y f l a t t e n e d s p h e r e s 3 LI large, with a
r o u g h s u r f a c e . X-ray d i f f r a c t i o n a l l o w s t o i d e n t i f y t h e s p h e r i c a l
c r y s t a l s a s ZSM-12. Some c h a r a c t e r i s t i c p i t s i n t h e ZSM-5 s u r f a c e
seem t o c o r r e s p o n d t o t h e o r i g i n a l l o c a t i o n o f d e t a c h e d s p h e r o i d a l
c r y s t a l s . The i n war d g r o w t h o f a c r y s t a l a f t e r i t s n u c l e a t i o n on
611
a n h e t e r o g e n e o u s s u r f a c e is a we1 -known p h e n o m e n o n . I t h a s b e e n
carefully described, for instance i n t h e case o f ZSM-5 n u c l e a t i o n
o v e r amorphous s i l i c a ( r e f . 8 ) .
A c h a n g e o f m o r p h o l o g y o f ZSM- 2 f r o m e u h e d r a l p r i s m s t o h i g h -
i n d e x s u r f a c e s p h e r e s i s s u c h a n u n u s u a l phenomenon t h a t i t
d e s e r v e s a comment. I t c o u l d b e e x p l a i n e d o n l y b y a s h a r p r i s e o f
s u p e r s a t u r a t i o n , as i f a p r e v i o u s l y confined source of s o l u b l e
s p e c i e s had b e e n made a c c e s s i b l e t o t h e s o l u t i o n . T h e h o p p e r p i t s
i n t h e (010) f a c e s o f t h e ZSM-5 c r y s t a l s p r o p o s e t h e c o r e o f t h e
ZSM-5 c r y s t a l s a s a p o s s i b l e s o u r c e o f more s o l u b l e s p e c i e s . U n d e r
t h i s h y p o t h e s i s , once t h e o u t e r l a y e r of (100) t w i n n i n g d i s s o l v e d ,
t h e r a p i d d i s s o l u t i o n o f t h e ( 0 1 0 ) f a c e s would i n c r e a s e t h e r a t e
o f g r o w t h o f ZSM-12 b e y o n d t h e t h r e s h o l d o f d e v e l o p m e n t o f h i g h -
index f a c e s from t h e e d g e s of t h e f l a t f a c e s .
The f i g u r e 3 c , r e p r e s e n t i n g t h e s o l i d a f t e r 20 d a y s o f
s y n t h e s i s , c l e a r l y shows t h e growth of t h e f l a t t e n e d s p h e r e s of
ZSM-12, t h e s h r i n k i n g o f t h e ZSM-5 c r y s t a l s a n d t h e d e e p e n i n g of
t h e hopper p i t s i n t h e (010) f a c e s of t h e l a t t e r .
CONCLUSIONS
C h e m i c a l and p h y s i c a l f a c t o r s a f f e c t t h e s e l e c t i v i t y o f
formation of t h e c r y s t a l l i n e p h a s e s t y p i c a l of t h e
tetraethylammonium m e d i a . The i s s u e of b o r d e r l i n e s i t u a t i o n s i n
w h i c h s e v e r a l p h a s e s c a n b e f o r m e d may b e d i r e c t e d b y t h e n a t u r e
of s o l i d s u r f a c e s p r e s e n t i n t h e s y n t h e s i s s y s t e m .
ACKNOWLEDGMENTS
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1 E . L . W a d l i n g e r , G . T . Kerr a n d a n d E . J . R o s i n s k i , C a t a l y t i c
c o m p o s i t i o n o f a c r y s t a l l i n e z e o l i t e , US P a t . 3 , 3 0 8 , 0 6 9 ( 1 9 6 7 ) .
2 J . P e r e z - P a r i e n t e , J . A . M a r t e n s and P.A. J a c o b s ,
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and K2O c o n t a i n i n g a l u m i n o s i l i c a t e g e l s , A p p l i e d C a t a l . , 31
( 1987) 35-64.
3 J . P e r e z - P a r i e n t e , J . A . M a r t e n s and P . A . J a c o b s , F a c t o r s
a f f e c t i n g t h e s y n t h e s i s e f f i c i e n c y o f z e o l i t e BETA f r o m
a l u m i n o s i l i c a t e g e l s c o n t a i n i n g a l k a l i and t e t r a e t h y l a m m o n i u m
i o n s , Z e o l i t e s , 8 (1988) 46-53.
612
Z . Gabelica, N . U e w a e l e , L . M a i s t r i a u , J . B . Nagy a n d E . G .
Derouane, D i r e c t i n g p a r a m e t e r s i n t h e s y n t h e s i s of z e o l i t e s
ZSM-20 and b e t a , ACS Symp. S e r i e s , 3 9 8 ( 1 9 8 9 ) 5 1 8 - 5 4 3 .
D.E.W. V a u g h a n , M . M . J . T r e a c y , J . M . Newsam, K.G. S t r o h m a i e r a n d
W.J. M o r t i e r , S y n t h e s i s a n d c h a r a c t e r i z a t i o n o f z e o l i t e SZM-20,
ibidem 544-559.
Y . F . C h u , P r o c e s s f o r ZSM-11 p r o d u c t i o n , US P a t . 4 , 8 4 7 , 0 5 5
(1989).
E . J . K o s i n s k i and M.K. R u b i n , C r y s t a l l i n e z e o l i t e ZSM-12, US
P a t . 3,832,449 (1974).
J . C . J a n s e n , C . W . R . E n g e l e n a n d H . v a n Bekkum, C r y s t a l g r o w t h
r e g u l a t i o n a n d m o r p h o l o g y o f z e o l i t e s i n g l e c r y s t a l s o f t h e MFI
t y p e , ACS Symp. S e r . , 398 ( 1 9 8 9 ) 2 5 7 - 2 7 3 .
J . B.Nagy, Ph. B o d a r t , H . C o l l e t t e , C . F e r n a n d e z , Z . G a b e l i c a ,
A . N a s t r o and R . A i e l l o , C h a r a c t e r i z a t i o n of c r y s t a l l i n e a n d
a m o r p h o u s p h a s e s d u r i n g t h e s y n t h e s i s o f (TPA,M)-ZSM-5 Z e o l i t e s
( M = L i , Na, K ) . J . Chem. S O C . F a r a d a y T r a n s . 1 , 85 ( 1 9 8 9 )
2749-2765.
10 F . D i R e n z o , F . Remoue, P . M a s s i a n i , F . F a j u l a , F . F i g u e r a s a n d
T . Des C o u r i e r e s , C r y s t a l l i z a t i o n k i n e t i c s o f z e o l i t e TON,
Zeolites, submitted.
11 C . S . Cundy, p e r s o n a l c o m m u n i c a t i o n .
12 I.Y. Chan a n d S . I . Z o n e s , A n a l y t i c a l e l e c t r o n m i c r o s c o p y (AEM)
o f C u b i c P z e o l i t e t o Nu-3 z e o l i t e t r a n s f o r m a t i o n , Z e o l i t e s , 5
( 1 9 8 9 ) 3-11.
13 E . d e Vos B u r c h a r t , J . C . J a n s e n a n d H . v a n Bekkum, O r d e r e d
o v e r g r o w t h o f z e o l i t e X o n t o c r y s t a l s o f z e o l i t e A, Z e o l i t e s , 9
( 1 9 8 9 ) 432-435.
14 F . F a j u l a , F . F i g u e r a s , C . Gueguen a n d R . D u t a r t r e , B i n a r y
z e o l i t i c s y s t e m s , t h e i r s y n t h e s i s a n d t h e i r u t i l i z a t i o n , US
P a t . 4,847,224 (1989).
15 F . F a j u l a , S . N i c o l a s , F . D i R e n z o , C . G u e g u e n and F . F i g u e r a s ,
K i n e t i c s and m e c h a n i s m o f c r y s t a l g r o w t h o f z e o l i t e o m e g a , ACS
Symp. S e r . , 398 ( 1 9 8 9 ) 4 9 3 - 5 0 5 .
16 R . B . L a P i e r r e , A . C . Kohrman J r . , J . L . S c h l e n k e r , J . D . Wood,
M . K . Kubin and W . J . R o h r b a u g h , T h e f r a m e w o r k t o p o l o g y o f
ZSM-12: A h i g h - s i l i c a z e o l i t e , Z e o l i t e s , 5 ( 1 9 8 5 ) 3 4 6 - 3 4 8 .
17 J . M . Newsam, M.M.J. T r e a c y , W . T . K o e t s i e r a n d C . H . d e G r u y t e r ,
S t r u c t u r a l c h a r a c t e r i z a t i o n of z e o l i t e b e t a , Proc. ti. S O C .
( L o n d o n ) A, 42il ( 1 9 8 8 ) 375-4135.
18 N.A. B r i s c o e , J . L . C a s c i , J . A . D a n i e l s , D.W. J o h n s o n , M.D.
S h a n n o n a n d A. S t e w a r t , Some a s p e c t s o f t h e s y n t h e s i s ,
c h a r a c t e r i z a t i o n a n d p r o p e r t i e s o f z e o l i t e Nu-2, S t u d . S u r f a c e
S c i . C a t a l y s i s 45A, E l s e v i e r , A m s t e r d a m 1 9 8 9 , 1 5 1 .
19 J . B . H i g g i n s , K.B. L a P i e r r e , J . L . S c h l e n k e r , A . C . Rohrman J r . ,
J . D . Wood, G . T . Kerr a n d W . J . R o h r b a u g h , T h e f r a m e w o r k topology
of z e o l i t e b e t a , Z e o l i t e s , (1988) 446.
G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 613
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
Ferrierite samples with Ga/GatAl compositions ranging from 0 t o 90% are
synthesized hydrothermally in the presence o f piperidine. The incorporation of
aluminium and gallium in the zeolite is monitored with 27Al, 29Si and 71Ga
MAS - NMR .
INTRODUCTION
The isomorphic substitution of A1 and Si by other elements in the framework
of zeolites is of considerable interest. For example, gallium zeolites possess
surface chemical properties which are different from those o f aluminosil icate
zeolites and have special catalytic properties, e.g. in LPG aromatization
(refs. 1 and 2). A number of (Si, Ga)-analogs o f (Si,Al)-zeolites have been
made by direct synthesis (see e.g. the references cited in ref. 3).
In this paper we report on the synthesis of aluminosilicate ferrierite
samples with extensive isomorphous substitution by Ga. We developed a new
synthesis method according to which alumino-galloferrierites can be obtained
with Si/(GatAl) ratio’s ranging from 7.1 t o 3.4. The gallium content of
alumino-galloferrierites can be considerably higher than the aluminium content
of aluminosilicate ferrierites, for which the lower limit of Si/A1 is ca. 6
(ref. 3).
EXPERIMENTAL
Synthesis mixtures with the following molar compositions are used:
23.3 Na20 : T2O3 : 46.5 Si02 : 18.6 CSHIONH : 976 H20
where T stands for Ga and Al. The Ga/(GatAl) fractions used were 0.0, 0.5,
0.75 and 0.9. The gels were prepared as follows. In a first solution NaOH
(Merck) was added t o waterglass (Merck) with stirring and then piperidine
(Aldrich) was added. The second solution, consisting o f A12(S04)3.18H20
614
s1
5 10 15 20 25 30 35 40 45 50 55
2e
5 10 15 20 25 30 35 40 45 50 55
2 e
5 10 15 20 25 30 35 40 45 50 55
2e
5 10 15 20 25 30 35 40 45 50 55
2e
Fig. 1. The XRD patterns o f samples S1-S4.
616
TABLE 1
T-atom c o mp os it i o n o f s y n t h e s i s m i x t u r e and f e r r i e r i t e p r o d u c t s
Sample S y nt h es i s q e l C r y s t a l 1 i z a t i o n Droduct
Ga/(GatAl ) Ga/(GatAl ) S i / ( G a t A l ) Si/(GatAl ) Ga/U.C. Al/U.C.
ICP ICP MAS NMR
D i r e c t evidence f o r t h e A1 and Ga i n c o r p o r a t i o n i n t h e f e r r i e r i t e s t r u c t u r e
i s f o und i n t h e 27Al and 71Ga MAS-NMR s p e c t r a , shown i n F igs. 3 and 4,
r e s p e c t i v e l y . The 2 7 A l resonance a t 54 ppm ( F ig. 3) and t h e 71Ga MAS-NMR s i g n a l
a t 152 ppm (F ig. 4 ) a r e c h a r a c t e r i s t i c o f a t e t r a h e d r a l environment.
The "Si MAS-NMR s p e c t r a o f t h e samples a r e shown i n Fig.5. and t h e
chemical s h i f t v a l u e s o f t h e "Si l i n e s summarized i n T able 2. The "Si
spectrum o f S4, which c o n t a i n s t h e l a r g e s t amount o f g a l l i u m (T able l),
c l e a r l y d i s p l a y s f i v e l i n e s c o r r e s p o n d i n g t o t h e f i v e p o s s i b l e Si(n(A1,Ga))
s t r u c t u r a l s urro u n d i n g s , w i t h 0 < n < 4. I n t h e 29Si s p e c t r a o f t h e S2 and S3
samples, which c o n t a i n i m p o r t a n t amounts o f b o t h aluminium and g a l l i u m , no
d i r e c t d i s c r i m i n a t i o n between Si(nA1) and S i (nGa) s i g n a l s c o u l d be made, s i n c e
no extra splittings in the Si(n(A1,Ga)) lines are observed (Fig.5).
Nev ert heles s , t h e n = 0 l i n e s have a tendency t o s h i f t t o l o w e r ppm values
when h i g h e r Ga l o a d i n g s a r e achieved ( Ta b l e 2); t h e chemical s h i f t v a l u e s o f
t h e Sil(Ga,Al) and SiZ(Ga,Al) l i n e s , f o r example, move u p f i e l d w i t h i n c r e a s i n g
g a l l i u m content .
T h i s i n f l u e n c e o f t h e presence o f Ga on t h e 2 9 S i chemical
s h i f t was a l s o observed i n o t h e r g a l l i u m s i l i c a t e s ( r e f s . 5 and 6 ) . Probably,
a homogeneous d i s t r i b u t i o n o f A1 and Ga i n t h e f e r r i e r i t e framework can be
assumed.
The Si/GatAl r a t i o s o f t h e samples were c a l c u l a t e d f r o m t h e i n t e n s i t i e s o f
t h e i n d i v i d u a l S i (n(A1 ,Ga)) 1 i n e s o f t h e d e convolut ed 29Si s p e c t r a (T able 1).
The r e s u l t s a r e i n agreement w i t h t h e r e s u l t s f rom ICP.
618
Fig. 3. The 2 7 A l MAS NMR spectra o f samples Sl-S4. The *’s indicate the
position o f the spinning side bands.
52
51
SiO(AI,Ga)
I
Sil(A1,Ga)
I
TABLE 2
2 9 S i chemical s h i f t s of S i (n(A1 ,Ga)) 1 i n e s i n f e r r i e r i t e .
a
M
0
'2 3 0
d
.-
0 20
c1
6
N
Irl
m
10
cd
c1
m
h o
6 0.00 0.25 0.50 0.75 1 .oo
Ga/(Ga+Al) in initial mixture
Fig. 6. The yield o f alumino-galloferrierite zeolite as function of the
Ga/(GatAl) fraction in the synthesis mixtures o f samples S1-S4.
120
100
9 80
v
cd 60
n
40
20
0
0 1 2 3 4 5 6 7 8
Al or Ga / (u.c.)
Fig. 7. The 27Al and 71Ga NMR line intensities versus their content per unit
cell in the samples Sl-S4.
622
CONCLUSIONS
The f e r r i e r i t e structure seems to be p a r t i c u l a r l y susceptible t o Ga
i n c o r p o r a t i o n . The l o w e s t Si/Ga r a t i o o f alumino g a l l o f e r r i e r i t e s o b t a i n e d i n
t h i s work i s ca. 4, whereas t h e S i / A l r a t i o s f ound w i t h a l u m i n o s i l i c a t e
f e r r i e r i t e s a r e equal t o o r l a r g e r t h a n 6. Traces o f aluminium seem t o be
necessary i n o r d e r t o c r y s t a l l i z e f e r r i e r i t e s w i t h h i g h g a l l i u m c o n t e n t s . The
g a l l i u m c o n t e n t o f alumino g a l l o f e r r e i r i t e s c o u l d n o t be q u a n t i f i e d w i t h 'lGa
MAS-NMR, even when u s i n g a s p i n n i n g f r e q u e n cy o f 15 kHz.
ACKNOWLEDGMENTS
The a u t h o r s acknowledge t h e Fl e m i s h NFWO and t h e B e l g i a n M i n i s t e r y f o r
Science P o l i c y f o r a r e s e a r c h g r a n t . J.A.M. and P.J.G acknowledge t h e F lemish
NFWO f o r a re s e a r c h p o s i t i o n as Research A s s o c i a t e and S e n i o r Research
A s s oc iat e , r e s p e c t i v e l y .
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1 J.R. Mowry, R.F. Anderson and J.A. Johnson, O i l Gas J., 83 (1985) 128.
2 H. Kitagawa, H. Sendoda and Y. Ono, J. C a t a l . , 101 (1986) 12.
3 B. S u l i k o w s k i and J. K l i n o w s k i , J. Chem. SOC., Chem. Commun., 1289 (1989).
4 P.J. Grobet, H. Geerts, M. T i e l e n , J.A. Martens and P.A. Jacobs, Stud.
S u r f . S c i . C a t a l . , 46 (1989) 721.
5 D.E. Vaughan, M.T. M e l c h i o r and A.J. Jacobson, i n : G.D. St uck and F.G.
Dwyer (Eds.), I n t r a z e o l i t e Chemistry, ACS Symp. Ser. 218 (1983) 231.
6 S. Hayashi, K. Suzuki, S. Shin, K. Hayamizu and 0. Yamamoto, B u l l . Chem.
SOC. Jpn., 58 (1985) 52.
7 P.A. Jacobs and J.A. Martens, Stud. S u r f . S c i . C a t a l . 33 (1987) 217.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 623
01991 Elsevier Science Publishers B.V., Amsterdam
M.Ii.EPBA?iX\', C.B.TP.GIYEV
L!.n4.C-AP.'l~f~h.(-:V,
Irlstitute of Inorganic a n d Fhysica.1 Ckemistry Gf t h e A zerbaijan S S R
Academy of S c i e n c e s , 370143 Baku., Narimanov p r o s p e c t 29, USSF
suR.I MAR 1-
T h e p e p e r clenlsi wit11 kiyclrotl-:errv. e.1 t l cLricfi.>r mation of artificial g k s s e s
into zeolite-.like silica.t€?s,systr?r~leticallS. studied.Syr.thetic mowntainite,teing
a n a n a l o g u e of prirrary n r i r e r a l , w a s p r o d u c e d for t l i e first tir!ic.Ffft:(.t:- (.I
vc:riijt .c I . ~c t c r s , i . e . t e r ~perclture,coricentration,g r a s s grading,nature o f s c l -
ver,t, solid plie.se/liquid p h a s e ratic, on p h a s e forniaticiri w a s c o x s i d e r e d .
Zeolite-.like n a t u r e of sodiuri hydros.ilica.te w e s p r o v e d by radiography.,
t h e r m o g r a ~ i m e t r i c u l , chenlical &nd electrorir;,icro..copic methc.-ds of irivesti -
g,i+tiCIr..
I i i T K ODUCTIOP I
Due to uriique s t r u c t u r a l p r o p e r t i e s a n d wide r a n g e of c h a - a c t e r i u t i c s
ze o lites a r e u s e d iri cateil)rtic, a d s o r p t i o r p r o c e s s e s a n d in vm-ious bran-
c h e s of ratiorial econoniy. To meet gron-irig dec;ands of nioderri t e c h r o l o -
gi cal p r o c e s s e s it i s n e c e s s a r y tG s t u d y a n d select n o v e l nELtLral Emcl
syrithetic alunmiriosilicate s,yster,is which c a n b e u s e d for production of
z eo lites witk? predeterniinec! crysteillirte s t r u c t u r e , compositior. e n d proper-
ties.
In t h e F r o c e s s of z e ol i t e s s y n t h e s i s natural a n d s y n t h e t i c alur.?iriosilica-
tt?s with c r) stallirie arid a ni orphous s t r u c t u r e ( t h e latter being p r e s e n t e d
by gels arid g$rsses) were used 2.5 an iritial s t c c k . High reactivity of
g l a s s e s b ein g ar. a m orphous material arid r i e c e s c i w of reproductiorl o f rla-
tural p r o c e s s . e s with a c t i ve Farticipatiori of n i i r . e r d s formation in labora-
tory, w ad e r e s e e . r c k e s to s t u d y thorotighly ra.w n.aterial.However,ccmplexi-
t-, a n d uristability of chemical c o n i p o s i t i o ~ ,i t s urivaria.Dilit4.,cryste.llic in-
clu.sioris, admixtLires iri natureil g l a s s e s turr-ed r e s e a r c h e s attention to
sy n th etic glasses.
A nuntber of w o r k s has b e e n d e v o t e d to crystellizatiori of zeolites
from v a r i o u s syr~tl-ieticg l a s s e s . O n e of t h e s e i s s y n t h e s i s of zeolite-like
si l icate, e.g. r h ode si t e - hydrosi l i c a t e of alkali a n d alkali-earth metetle.WE
h a v e p r c d L . c e c i two syr:thetic forms-K- a n d Na-rhodesits.It must Ire r.otec!
that z.ccordir.g to its, s t r u c t u r e mountainite a s well a s r h o d e s i t e could b e
r e g a r d e d as n:irierel of c.elhq:elite grc'up.
624
TABLE 1.
- ~ -
N a m e of Chemical composition Lattice p r r a m e t e r s , A Space
mirt e r a1 group
a b C
-_____ ------- -- I - - - - - ---
&odesite KNa[ Ca2Si8019 ( H 2 0 ) 2] 4 H 2 0 23,8 6,54 7,05 Pnin2
Hydrcdel-
hayelite KF (H 2 0 ) 44H20
C2 ( S I N ) 7039 6,65 23,84 7,07 Pmri2
4 2
Mountainte K 2 N a 2 k a 2 S i g ) 03 9 ( O H ) 2] 4 H 2 0 3 3,51 13,51 13,51 Pniri2
r a c g e of reflection a n g l e s 8 = 2 - 70
0
. Angles m e a s u r e m e n t accuracy
w a s of -
+ o
0.1 .
Thermogravimetrical a n a l y s i s of t h e s a m p l e s was c a r r i e d out in dyna-
mic mode with t h e u s e of “(3- Derivatograph 1500-D” of Eiurigariari firm
MOM. T e m p e r a t u r e r a n g e w a s within 20
0
- 1000°C.
0
S u r v e y conditi0ns:heating r a t e i s 10 /min ; pa.per t r a v e l s p e e d is 2,s nim/
RE; SUL’I’S
Diffredonietry d a t a for synthetic rrokntainite (Table 2 )
d a t a for i t s n a t u r a l a n a l o g u e /ref. .?I.
TARLE: 2.
Ciffrectometr)- d a t a f a r s y n t h e t i c moLnteir.ite ar.d i t s thermally t r e s t e d
C
( a t 370 C ) fvrr.;.
---
Mourlttrinite --
0
d A0 J P. J
exp I dexp 9
13,18 90 11, 24 46
6,58 90 6,38 6
6,OO 16 5, 7 8 52
5, 59 14 4, 3 6 8
4,72 62 4, 06 1c
4,18 44 3,9 2 5
3,76 16 3, 06 21
3,62 11 2, e9 26
3,41 25 2, 7 7 16
3,22 13
3,04 21
2,92 100
627
2, 84 36
2, 70 18
2, 34 23
1, 96 32
1, 74 22
TABLE 3.
Ccnditions a n d crq.stallizetiori p r o d u c t s of silica- r i c h g l a s s i r NaOH ar.d
N a 2 C 0 3 so1utior.s
' 0
reflections d = 13,18; 6,58; 3,22 A were observed.
R e v e r s i b l e chare.cter of dehydration, ion-exchange ability, p r e s e n c e
of specific cavities, c h a r a c t e r r i s t i c for z e o l i t e s , in tkje s t r u c t u r e cor.firr.
that rr.otir.tainite b e l o c g s to s i l i c e t e s having z e o l i t e s piroperti es.
R E F E R E N CE S
r h o d e s i t e a n d mountainite" .
3. J. P. C-ard, H. F. W. Taq-lor, "An irivcstigation of tvro r e w minerals:
Mireral. Was., 1957, V. 31, p. 611-623
SUMMAKY
The state of iron in microporous ferrisilicates with MFI -
structure as well as in template free synthesized FeZSM-5 zeolites
has been examined by XRD, IR, ESR, Si MAS NMR, ammonia TPD, and
catalysis. The percentage of iron in the ferrisilicate framework
could reliably be determined by two independent methods, ammonia
TPD and Si MAS N M R . Catalytically, the Fe related acid sites are
weaker than those of the parent ZSM-5 but. nevertheless, they
isomerize m-xylene and convert ethylbenzene. Nonframework iron
dehydrogenates ethylbenzene to styrene, where the selectivity
correlates with the amount of nonframework iron.
INTRODUCTION
One possibility to modify the acidic and catalytic properties of
zeolites and zeolite-like metallosilicates (1) consists in varying
their chemical composition at the stage of synthesis.
Advantageously, this a1 lows the tailored design of active
molecular sieve components via substitution of A1 or Si by several
elements (e. 8 . E, Ga, Cr, V, Co, and others) ( 1 - 15). Iron
containing zeolites or pure ferrisilicates with MFI structure are
of special interest as catalysts for the conversion of several
aromatic compounds, above a l l C 8 nlkylaromatics. Numerous
investigations have been performed in order t o confirm the
incorporation of iron into the molecular sieve framework and to
reveal the nature of iron in both framework and nonframework
positions (1,16 - 2 6 ) . Incontestably, the location and the state of
iron are essentially for their acidic, catalytic and
shape-selective properties. But the knowledge about the exact
distribution of iron between the lattice and channels is still
incomplete. Therefore, this contribution emphasizes the
quantitative determination of iron throughout the matrix of
aluminum free ZSM-5 type ferrisilicates. The consequences for the
aciditiy and catalytic activity of the samples are discussed and
the results are related to reference samples such as iron
632
EXPERI MENTAL
Samale w&am.Lu?n
. . .
- . .
( i ) Perrlslllcates ( F e S i 1 ) . T h e A 1 f r e e f e r r i s i l i c a t e s with
Z S M - 5 s t r u c t u r e were s y n t h e s i z e d b y m X i n g a n a c j.d s o l u t i o n of
i r o n s u l f a t e w i t h h a l f t h e v o l u m e of a s o d i u m s i l i c a t e s o l u t i o n a t
room t e m p e r a t u r e . An a q u e o u s s o l u t on o f tetrapropylammonium
bromi de and t h e r e m a i n d e r o f t h e d i l u t e d so d iu m s i l i c a t e s o l u t i o n
were a d d e d t o t h e r e s u l t i n g g e l ( a f t e r a n a g i n g p e r i o d o f 1 h ) . T h e
mixture w 3 s s t i r r e d f o r 1 h, then placed i n a t e f l o n coated
s t a i n l e s s s t e e l a u t o c l a v e an d k e p t u n d e r a u t o g e n o u s p r e s s u r e a t 4 4 3
K f o r 48 h . The r e s u l t i n g w h i t e o r p a l e y e l l o w s o l i d was filtered,
washed a n d d r i e d a t 383 K . T h e t e m p l a t e was removed b y calcination
a t 773 K f o r 7 h i n a i r f o l l o w e d b y a t h r e e f o l d e x c h a n g e o f Na'. by
NH4+ i . o n s a t 353 K for 2 h . AAS was u s e d f o r a n a l y s i s ( T a b l e l a ) .
. .
( i i j E.e contalnlna Z S M - 5 0 . Ferric nitrate, sodium
a l u m i n a t e , s i l i c a s o l a n d s o d i u m h y d r o x i d e were used as starting
materials f o r t h e s y n t h e s i s . S i l i c a s o l was added to a diluted
solution containing the aluminate, t h e sodium hydroxide a nd the
f e r r i c n i t r a t e . T h e m o l a r r a t i o s o f t h e c o m p o n e n t s were: 2-8 N a g O *
(Al2O3+FezO3j * 3 0 - 9 0 S i Oz *
6 0 0 - 2 , 5 0 0 HzO. The r a t i o Fe 203 : A 1 2 0 3
was v a r i e d b e t w e e n 0 . 1 a n d 0 . 8 . Th e c r y s t a l l i z a t i o n o f t h e z e o l i t e s
was p e r f o r m e d h y d r o t h e r m a l l y u n d e r a u t o g e n e o u s p r e s s u r e w i t h i n 8 -
24 h a t 4 5 3 - 4 8 3 K . T h e a d d i t i o n of s e e d c r y s t a l s ( a b o u t 3 w t . % of
ferrisilicate) was f o u n d t o b e n e c e s s a r y f o r p r o m o t i n g the
c r y s t a l l i z a t i o n p r o c e s s . Ho wev er , n o o r g a n i c t e m p l a t e was n e e d e d .
The r e m o v a l o f Na+ cations in the as-synthesized products was
a c c o m p l i s h e d b y i o n - e x c h a n g e ( T a b l e l b ) . T h e f i n a l ammonium f o r m o f
t h e z e o l i t e s c o n t a i n e d less t h a n 0 . 1 w t . % N a p O . T h e d e s i g n a t i o n of
t h e samples is t o be read as HFeSil for the H form of the
f e r r i s i l i c a t e s r e s p . HFeZSM-5 f o r t h e i r o n c o n t a i n i n g z e o l i t e s . The
a n a l y t i c a l (Si0z/Fez03)z r a t i o s are g i v e n i n p a r e n t h e s e s .
( i i i ) Reference samples.A c o m m e r c i a l ZSM - 5 p r o d u c t (HS 3 0 ,
C h e m i e - AG Bitterfeld) i n t h e H form a s well a silicalite
as
i m p r e g n a t e d w i t h a F e( N0 3 ) 3 s o l u t i o n t o r e a c h a n i r o n c o n t e n t o f 1
w t . % a f t e r c a l c i n a t i o n ( 7 7 5 K , 2 h ) were u s e d a s reference (Table
lb).
633
TABLE 1
List of samples and characterization data
a) ferrisilicates
a
NH3 desorbed T~(KP
Overall Htpd
Sample ( sio2)
Fe203 E
( sio2
Me203
fe203
Z A1203
1 cXRDe
Z
NH3 desorbedb
Overall Htp
d Tm(K)'
SamDle characterization
The XRD data were obtained with a HZG 4 diffractoineter by using
qi-filtered Cu K, radiation. IR spectra were recorded with a
Specord M 85 (Zeiss Jena) using the KBr pellet technique. ESH
measurements were performed with a ZWG ERS - 220 X - band
634
s p e c t r o m e t e r a t 7 7 an d 2 9 5 K. T h e 2 9 S i HAS N M K s p e c t r a were
measured with a B r u k e r MSL 400 s p e c t r o m e t e r a t a r e s o n a n c e
f r e q u e n c y o f 7 9 MHz u s i n g s i n g e - p u l s e e x c i t a t i o n w i t h high-power
p r o t o n d e c o u p l i n g . NH3-TPD m e a s u r e m e n t s were c a r r i e d o u t a t n o r m a l
3
p r e s s u r e i n a f l o w r e a c t o r w i t h He a s c a r r i e r g a s ( f l o w r a t e 1 cm
s - l j c o n t a i n i n g 3 Vo1.X o f NH3. T h e h e a t i n g r a t e a m o u n t e d t o 12 K
min-l. Sample w e i g h t s of 200 mg were used (mesh size 25-60).
Details are g i v e n e l s e w h e r e ( 2 9 ) .
B d s o r D t i q n and catalvsis
A f t e r a c t i v a t i o n in VUCUO ( p < = Pa, T = 570 K , t > = 5 h)
t h e f e r r i s i l i c a t e s were c h a r a c t e r i z e d b y i s o t h e r m a l a d s o r p t i o n a nd
d e s o r p t i o n of n-hexane (T = 293 K , 0.02 <= p/p
S
<= 0.9, ps
saturation pressure) using a McBain balance. The crystallinity
parameter CAds was e s t i m a t e d b y r e f e r r i n g the experimental
s a t u r a t i o n v a l u e a t p/p, = 0 . 5 t o t h e c a l c u l a t e d m i c r o p o r e v o l u m e
3
o f a n i d e a l MFI s t r u c t u r e ( 0 . 1 9 cm / g > . A d s o r p t i o n d a t a f o r b e n z e n e
a n d water o f t h e template f r e e synthesized Fe-ZSM-5 samples are
reported i n Ref. ( 2 9 ) .
Both t h e conversion of ethylbenzene and the isomerization of
m - x y l e n e were c a r r i e d o u t i n a fixed-bed, continuous glass
flow
r e a c t o r ( 2 cm i n t e r n a l d i a m e t e r ) a t a t m o s p h e r i c p r e s s u r e a n d a
s t a n d a r d f l o w r a t e o f 1 0 1 h-' h y d r o g e n , l o a d e d w i t h 1 V o 1 . X of t h e
o r g a n i c s u b s t r a t e . I n e i t h e r case 1 8 : of t h e b i n d e r - f r e e zeolite
p o w d e r i n i t s H f o r m was u s e d ( m e s h s i z e 2 5 t o 6 0 ) . D e t a i l s c a n b e
f o u n d i n Ref. ( 2 9 ) .
s t r u c t u r e i s c o n f i r m e d by t h e r e s u l t s o f n - h e x a n e adsorption (cf.
T a b l e 1 ) . T h e v a l u e s o f t h e r e a l m i c r o p o r e volum e f o r m o s t of the
samples were f o u n d t.0 be near the theoretically calculated pore
v o l u m e o f a n i d e a l MFI s t r u c t u r e ( 0 . 1 9 cm 3/ g ) . T h e h i g h v a l u e s o f
t h e c r y s t a l l i n i t y parameter C A c o n f i r m the successful synthesis.
The low Cads v a l u e o f H F e S i l ( 5 0 8 ) o b v i o u s l y comes a b o u t b y t h e low
a d s o r p t i o n c a p a c i t y of t h e a l i e n quartz phase. Figure 1
d e m o n s t r a t e s t h e m o d i f i c a t i o n of t h e u n i t c e l l volume w i t h t h e i r o n
c o n t e n t . A t i n c r e a s i n g i r o n c o n c e n t r a t i o n ( d e c r e a s i n g (Si02/Fe203)=
r a t i o s ) t h e u n i t c e l l is expanded d u e t o t h e different length of
t h e S i - 0 and F e - 0 b o n d s . This r e s u l t p r o v e s t h e i n c o r p o r a t i o n o f a t
l e a s t a c e r t a i n p a r t o f i r o n atoms i n t o t h e l a t t i c e . S z o s t a k e t al.
(21) found similar r e s u l t s f o r a n a l o g o u s f e r r i s i l i c a t e s .
1 2
I
3 Fe/UC
-
F i g . 2 . D e p e n d e n c e o f t h e wavenumber v f o r t h e T-0-T vibration on
t h e i r o n c o n t e n t per u n i t c e l l F e / u . c .
-
Sic)?/Pe 0
2'3
f r a m e w o r k r a t i o i n f e r r i s i l i c a t e s is e x p l a i n e d by help
of F i g u r e 5 which shows a typical "Si MAS NMR spectrum of a
f e r r i s i l i c a t e s a m p l e . Two s i g n a l s c a n b e d i s t i n g u i s h e d : a n i n t e n s e
a s y m m e t r i c l i n e a t a h o u t -113 ppm w h i c h i s c a u s e d b y s i l i c o n a t o m s
637
655
0 2 4 6 8 10 12 11 16 18
Overall iron content
(Fe203/Si02) x lo3
4
bonded via oxygen to four other silicon atoms (Q ( O F e ) ) ( 3 1 ) and a
shoulder at about -104 ppm which is assigned to silicon atoms
4
surrounded by three other silicon atoms and one iron atom (Q (1Fe))
(20). An evaluation of the Si02/Fe203 framework ratio is based on
the relative intensities of these two signals but has to account
3
for the fact that silanol groups in silicalite (Q (OFe)) exhibit a
resonance line at the same position o f -104 ppm as the
638
I I . l , l l l l , l, , I , I , , , , I , , , I, , , , , I , , , , , , , , I , , ,
TABLE 2
Quantitative "Si MAS NMR data f o r some ferrisilicates
F i g . 6 . C o m p a r i s o n b e t w e e n t h e d a t a f o r t h e SiO / F e 0 f r a m e w o r k
2 2 3
r a t i o o b t a i n e d f r o m N H 3 TPD ( X ) an d "Si MAS NMR ( 0 )
UCiiLx
F i g u r e 3a s h o w s t y p i c a l TPD s p e c t r a of a n HZSM-5 z e o l i t e (curve
l ) , a n HFeZSM-5 z e o l i t e ( c u r v e 2 ) an d a ferrisilicate (curve 4).
TPD s p e c t r a o f f e r r i s i l i c a t e s with different iron contents are
p r e s e n t e d i n F i g . 3b ( c u r v e s 3-7). Characteristically, both the
o v e r a l l c o n c e n t r a t i o n o f a c i d s i t e s an d t h e a m ount o f B r a n s t e d a c i d
s i t e s d e c r e a s e d i s t i n c t l y f o r samples with comparable Si02/Fe203
r a t i o s when t u r n i n g f r o m HZSM-5 t o t h e H F e S i l samples (Table 1).
S i m u l t a n e o u s l y , t h e maximum p o s i t i o n f o r t h e h i g h t e m p e r a t u r e peak
s h i f t s t o i o w e r v a l u e s ( F i g . 3 a ) . W i t h i n t h e HFeZSM-5 series Ccf.
T a b l e l b ) t h e d i m i n u t i o n of t h e o v e r a l l a c i d i t y a n d o f the a m ount
of Brprnsted centres with increasing iron content is small.
N e v e r t h e l e s s , t h e maximum p o s i t i o n o f the high temperature €leak
c h a n g e s t o l o w e r v a l u e s . F o r t h e H F e S i l samples t h e o v e r a l l a c i d i t y
as w e l l a s t h e amount o f Brprnsted a c i d s i t e s d e p e n d on t h e
(Si02/FeL03)t r a t i o , although the a c i d i t y does not change
r e m a r k a b l y w i t h i n t h e r a n g e f r o m 5 8 t o 9 4 . ( c f . F i g . 3 b a nd T a h l r
1 ) . A small s h i f t i n t h e maximum p o s i t i o n o f t h e high temperature
p e a k i s a ss u m e d t o l i e i n t h e m a r g i n of e r r o r . Thus, if iron is
s u b s t i t u t e d f o r aluminium b o t h t h e number a nd strength of acid
s i t e s , e s p e c i a l l y t h a t of Brmnsted a c i d c e n t r e s are i n f l u e n c e d .
640
b t a l v t i c erooerties
The activity of the samples shown in Figure 7 follows the same
sequence as the concentration of strong acid centres revealed by
NH3 TPD, U L Z . HZSM-5 > HFeZSM-5 > HFeSil. The iron-impregnated
silicalite does not possess isomerization activity, but converts
ethylbenzene at T > 675 K, yet to a minor extent (5 X at 775 K).
Within the ferrisilicates series the sample HFeSil(58) with the
highest Fe content shows t,he highest activity. It is, however, low
in comparison to the parent ZSM-5 (especially for the ethylbenzene
conversion). The lower activity may primarily be attributed to the
lower concentration of framework acid sites (theoretically 3 . 2 Fe 3+
per unit cell in case of the ferrisilicates compared to
approximately 4.6 A13+ per unit cell in case of ZSM-5).
-s 60
- 50
5 40
._
Ln
& 30
5 20
10
I
10 20 30 40 50
m- Xylene Conversion (YO1
. .
shaee s e l e c t i v i t s
During the isomerization of m-xylene catalysts with shape
selective properties maintain p/o-isomer ratios higher than
p r e d i c t e d by thermodynamics. Th e isomer ratio depends on the
m-xylene c o n v e r s i o n ( 3 0 ) . I t is e v i d e n t ( F i g . 8 ) that the HZSM-5
sample sh o w s t h e s t r o n g e s t s h a p e s e l e c t i v i t y f o l l o w e d b y HFeZSM-5.
The p u r e f e r r i s i l i c a t e s e x e r t o n l y weak selective e f f e c t s .
shape
The d a t a seem t o i n d i c a t e a s l i g h t i n c r e a s e with
decreasing iron
c o n t e n t s . This c o n t r a d i c t s c u r r e n t i d e a s t h a t f e r r i s i l i c a t e s should
r e v e a l h i g h e r s h a p e s e l e c t i v i t y d u e t o t h e nonframework i r o n which
i n e v i t a b l y is p r e s e n t a f t e r s y n t h e s i s a nd w h i c h r e n d e r s mure
d i f f i c u l t t h e mass t r a n s p o r t i n s i d e t h e p o r e s y s t e m . I n t h e p r e s e n t
c a s e a l l i n v e s t i g a t e d s a m p l e s h a v e ZSM-5 s t r u c t u r e w h e r e t h e p o r e
d i a m e t e r s h o u l d b e t h e same. Th e e n l a r g e m e n t o f t h e u n i t c e l l
dimensions as observed f o r t h e f e r r i s i l i c a t e s should b e n o t great
e n o u g h a s t o e x p l a i n t h e d i f f e r e n t s h a p e s e l e c t i v i t i e s . The c o k e
d e p o s i t i o n c a n n o t b e t h e r e a s o n s i n c e more c o k e i s f o r m e d on t h e
f e r r i s i l i c a t e s a s a l r e a d y i n f e r r e d f r o m v i s u a l i n s p e c t i o n . REM
p h o t o g r a p h s s h o w , h o w e v e r , t h a t t h e ZSM-5 h a s t h e l a r g e s t c r y s t a l
s i z e f o l l o w e d by t h e F e a n a l o g u e s . Large c r y s t a l s d o n o t o n l y
642
DehvdruaenationQ€ethvlben,ene
7 indeDendenceQnucontentnf
nonframeworkksDecies
Since t h e iron impregnated s i l i c a l i t e has no Fe in framework
p o s i t i o n s t h e a c t i v i t y observed f o r t h e c o n v e r s i o n of ethylbenzene
originates from nonframework Fe species. These species
dehydrogenate ethylbenzene t o s t y r e n e ( F i g . 9). The relationship
b e t w e e n t h e s t y r e n e s e l e c t i v i t y an d t h e n o n f r a m e w o r k iron content
is n o n l i n e a r . O b v i o u s l y , n o t o n l y t h e c o n c e n t r a t i o n o f n o n f r a m e w o r k
Fe b u t also its dispersity determines the extent of styrene
f o r m a t i o n . A similar r e l a t i o n s h i p between styrene formation from
-:bvlbenzene an d t . h e o v e r a l l iron content is reported for the
P i g . 9 . S t y r e n e s e l e c t i v i t y enhancement w i t h i n c r e a s i n g c o n t e n t of
nonframework i r o n i n t h e ferrisilicate series for two reaction
temperatures. (0) 673 K , ( 0 ) 773 K.
643
CONCLUSIONS
Microporous f e r r i s i l i c a t e s , synthesized with Si02/Fe203 ratios
o f 58 - 5 0 8 , i n c o r p o r a t e i r o n t o a p e r c e n t a g e > 80 % only at low
i r o n c o n c e n t r a t i o n s an d w i t h i n c r e a s i n g a m o u n t s o f q u a r t z ( u p t o 30
X). At higher iron content the part of nonframework species
i n c r e a s e s u p t o 50 % . I r o n i n framework p o s i t i o n s e n l a r g e s t h e u n i t
c e l l v o l u m e and s h i f t s the T-0-T vibration frequency to lower
v a l u e s . Si0H:Pe B r e n s t e d s i t e s are weaker t h a n Si0H:Al sites. The
c a t a l y t i c a c t i v i t y f o r t h e t e s t r e a c t i o n s is directly related to
t h e c o n c e n t r a t i o n of Brensted sites. N onfra m e w ork iron species
dehydrogenate ethylbenzene t o s t y r e n e t h e formation of which can
t h u s be t a k e n a s evidence for the presence of these species.
Template-free synthesized FeZSM-5 zeolites show intermediate
p r o p e r t i e s c o m p ar ed t o t h e p a r e n t ZSM-5 a nd t h e f e r r i s i l i c a t e s . T h e
A 1 r e l a t e d a c i d s i t e s of FeZSM-5 zeolites decide the catalytic
p r o p e r t i e s predominantly.
ACKNOW LEDGEMENT
The a u t h o r s g r a t e f u l l y ack n o wl ed g e t h e supply of FeZSM-5 and
s i l i c a l i t e samples b y Dr. U . H P d i c k e ( C h e m i e AG B i t t e r f e l d ) a n d by
Dr. B . F a h l k e ( I n s t . I n o r g . C h e m . ) , resp., a nd s u p p o r t by Dr. M.
H u n g e r ( U n i v e r s i t y of L e i p z i g , 'H MAS N H R ) , Mr. J. Richter-Mendau
(REM), D r s . H . K o s s l i c k ( S y n t h e s i s ) and J . Janchen ( A d s o r p t i o n ) .
REFERENCES
1 R . S z o s t a k , Molecular s i e v e s : P r i n c i p l e s of S y n t h e s i s and
I d e n t i f i c a t i o n (Van N o s t r a n d R e i n h o l d New Y o r k , 1989), 205.
2 B . U n g e r , T h e s i s , TH " C a r l S c h o r l e m m e r " M e r s e b u r g , 1 9 8 8 .
3 S . R . E l y , M . H . K l o t z . Belg. P a t . 8 8 0 8 5 8 ( 1 9 8 0 ) .
4 M . Taramasso, G. Perego, B . N o t a r i , P r o c . 5 t h I n t e r n . Conf.
Z e o l . , London 1980, 4 0 .
5 M. T i e l e n , M . G e e l e n , P . A . J a c o b s , P r o c . I n t e r n . Symp. Z e o l .
C a t a l . , S i o f o k 1 9 8 5 . 1.
6 C . T . W . Ch u , C . D . C h a n g , J . P h y s . Chem. 89 ( 1 9 8 5 ) 1 5 6 9 .
644
SUMMARY
Zeolite ZSM-57 can be synthesized from sodium-containing alumosilicate els using
%
hexaethyl-C5-diquatas organic template and silica sol as silica source. ZSM-57 can e readily
distinguished from the structurally closely related zeolites with the FER framework topology
by its X-ray powder attern and mid-infrared spectrum. From thermogravimetric analysis of
as-synthesized ZSM-!7 it follows that a plying an air calcination at 550 "C for several hours is
P
sufficient to remove the organic temp ate from the pores of the zeolite. The results of two
selected test reactions for probing the effective pore width of zeolites, viz. ethylbenzene
dis ro ortionation and n-decane isomerization su est that the pore width is lar er for
ZSb-f7 as compared to ZSM-35 (ferrierite) and 8 M - 5 . This is in agreement wit8; their
crystallographic structures and offers new opportunities in shape selective catalysis and
molecular sieve separation.
INTRODUCTION
ZSM-57 is a medium pore, high silica zeolite with a structure very similar to ferrierite
(refs. 1,2). Both zeolites possess channel systems consisting of intersecting linear eight-
membered and ten-membered ring pores. However, the ZSM-57 framework contains four-
membered rings which are not present in ferrierite (refs. 1,2). Interestingly, the structure of
ZSM-57 appeared in a systematic derivation of hypothetical structures based on the
ferrierite net (ref. 3).
Although the apertures of the eight-ring channels in ZSM-57 and ferrierite are of a
comparable size (0.33 x 0.48 nm versus 0.35 x 0.48 nm), the ten-ring channels are significantly
larger in the former zeolite (0.51 x 0.58 nm versus 0.42 x 0.54 nm) (refs. 1,2), and they are
even slightly larger than the sinusoidal (0.51 x 0.54 nm) and the linear (0.54 x 0.56 nm)
channels in zeolite Z S M J (ref. 4). Hence, from their crystallographic structures differences in
the shape selective properties of these zeolites can be expected.
The hydrothermal synthesis of zeolite ZSM-57 was first described by Valyocsik et al.
(ref. 5 ) from sodium containing alumosilicate gels using N,N,N,N,N,N - hexaethylpenta-
methylenediammoniumdibromide (hexaethyl-C5-diquat) as organic template. Here we report
on our attempts to synthesize zeolite ZSM-57, and on its characterization by X-ray powder
diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TGA), mid-
infrared- (IR-) spectroscopy and selected catalytic test reactions. For comparison, data
-
obtained with a material of the FER structure type, viz. ZSM-35, are also included.
646
EXPERIMENTAL
The template required for the synthesis of zeolite ZSM-57 was prepared by refluxing
1J-dibromopentane and a surplus of triethylamine in ethanol as solvent for several hours
(ref. 5). After cooling the mixture with an ice bath, a white solid precipitated which was
recovered by filtration, washed with diethylether und then used for the synthesis experiments
without further purification. As silica sources, either sodium waterglass (Merck; 28.5 wt.-%
Si02, 8.8 wt.-% Na20, ca. 62.7 wt.-% H20) or colloidal silica sol (Ludox HS-40, DuPont;
40 wt.-% Si02 in water) were used. All synthesis experiments were conducted at 160 "C and
the crystallization time was restricted to 6 days. After this time the autoclaves were quenched
in cold water and the solid products recovered by filtration, washed with distilled water and
dried at 120 "C. Characterization of the as-synthesized materials occurred by X-ray powder
diffraction (Cub-radiation; 40 kV, 30 mA) and IR-spectroscopy in the region of the lattice
vibrations using the KBr pellet technique. The product of an optimized synthesis was further
subjected to scanning electron microscopy and thermogravimetric analysis.
HZSM-57 was obtained by calcining the as-synthesized material for 16 hours at 540 "C in
air, followed by an ion exchange with a 1 n aqueous solution of NH&l and a second air
calcination for 16 hours at 350 "C. The bifunctional form (HZSM-57 loaded with 0.27 wt.-%
of palladium) was prepared via an optimized procedure which has been described previously
(ref. 6). For a characterization of the shape selective properties of ZSM-57, two established
test reactions, viz. the disproportionation of ethylbenzene (ref. 7) and the bifunctional
conversion of n-decane (ref. 8) were selected. Both reactions were performed in a flow-type
apparatus with fixed bed reactor under atmospheric pressure. The partial pressures of the
feed hydrocarbons ethylbenzene (E-Bz) or n-decane (n-De) amounted to pHC= 1.3 kPa.
Nitrogen or hydrogen was used as the carrier gas with ethylbenzene or n-decane as feed,
respectively. Product analysis was achieved by automatic sampling and on-line analysis via
temperature programmed capillary glc.
For a comparison of zeolite ZSM-57 with materials of the ferrierite structure, zeolite
ZSM-35 was synthesized according to a published method using 1,Zdiaminoethane as
template (ref. 9).
a ferrierite material or the structurally related zeolite ZSM-57. However, if sodium waterglass
is replaced by colloidal silica sol as the silica source, pure ZSM-57 was obtained after 6 days
at 160 "Cfrom a gel with the composition: Si02/A1203 = 60, H20/Si02 = 40, Na+/Si02 =
0.6,OH-/Si02 = 0.1 and R/Si02= 0.1. Note that in this case no sulfuric acid was required to
adjust the pH, instead a concentrated aqueous solution of NaOH was added. This example
demonstrates that, like in numerous other zeolite syntheses, the nature (reactivity) of the
silica source plays an important role in directing the structure of the crystallizing material.
The X-ray powder pattern of as-synthesized zeolite ZSM-57 is shown in Figure 1 (upper
part). The agreement of line positions and relative intensities with literature data (ref. 5) is
very good. However, ZSM-57 and ZSM-35 can be readily distinguished on the basis of their
X-ray powder patterns: The most significant differences are the presence of an additional
reflexion of zeolite ZSM-57 around 7.5 degrees 2 8 and the absence of a peak of medium
I I I I I I I I
ZSM-57
>
k
v) 5 10 15 20 25 30 35 40 45 50
Z
w
I- I I I I I I I I
-
Z
5 10 15 20 25 30 35 40 45 50
ANGLE 28 , d e g
Fig. 1. X-ray powder patterns of as-synthesized zeolites ZSM-57 and ZSM-35 (Cub-
radiation; 40 kV, 30 mA).
648
intensity at ca. 14 degrees 2 8 . Indeed, it was stated in the original patent (ref. 5) that due to
the latter difference, ZSM-57 can be "readily distinguished from ferrierite-type zeolites, such
as ZSM-35".
Mid-infrared spectra of ZSM-57 and ZSM-35 are depicted in Figure 2. The pattern for
ZSM-35 essentially agrees with those published in the literature (refs. 11,12). The pattern for
ZSM-57 is reported here for the first time. Both zeolites have two characteristic absorption
bands around 1230 cm-1. These two bands can be assigned to the vibrations of five-membered
oxygen rings (refs. 12,13), which is in agreement with the crystallographic structures of both
materials. Slight shifts in the frequency of each IR-band may be explained by the unique
framework structure of every zeolite (ref. 14). One significant difference between both
zeolites appears in the region around 600 cm-1, which is known to be sensitive to structural
changes (ref. 15). Whereas ZSM-35 shows a single band in this range, ZSM-57 possesses a
doublet. This additional band may be tentatively assigned to the presence of four-membered
rings in the structure of the latter zeolite (ref. 1,2) which are absent in the ferrierite
framework. Hence, in addition to X-ray powder diffraction, IR-spectroscopy also offers a
means to distinguish between both zeolites.
60
55
50
45
40
35
30
25
20
15
10
5
1400 1200 1000 800 600 40 0
60
55
50
45
40
35
30
25
-1
WAVE NUMBER , c m
Fig. 3. Scanning electron micrograph of zeolite ZSM-57. The white scale bar corresponds to
10pm.
100
M 95
I--
I
c,
LLJ 90
B
85
80 '
0 70 140 210 280 350 420 490 5 6 0 630 7 0 0 770
Temperature, O C
Fig. 4. Weight-loss of as-synthesized ZSM-57 upon heating from room temperature to 770 "C
(rate: 5 K/min) in an air flow ($air = 50 cm3/min). Full line: Sample weight in dependence of
temperature, dotted line: first derivate of that curve.
650
M 12 75
L
i T = 250 "C
n 10 = 200 gh/mol-
-1
- W/FE-,z
= 0.2 g
W
-
>. 8 50
IY
0
t
X
6
Z
0
- 4 25
cn
of
W
> 2
0 2 4 6 8 1 0 0 2 4 6 8 1 0
TIME ON STREAM, h
~ 1.3 kPa, PN2 = 100 @a.
Fig. 5. Disproportionation of ethylbenzene in HZSM-57; P E - B=
ref. 19), this indicates a larger effective pore width of ZSM-57 compared to ZSM-5 or
ZSM-35, which is in good agreement with the structures of these zeolites.
CONCLUSIONS
Provided that the right silica source is used, ZSM-57 can be readily synthesized with the
hexaethyl-C5-diquat cation as organic template. It can be readily distinguished from the
structurally very closely related zeolites with the FER structure-type, e. g. ZSM-35, on the
basis of their X-ray powder patterns and mid-infrared spectra. Thermogravimetric analysis
revealed that, like with many ofther high-silica zeolites, the template occluded inside the
pores during synthesis can be readily burned off by air calcination for several hours at 550 "C.
According to the results of selected catalytic test reactions the effective pore width of zeolite
ZSM-57 is larger than that of ZSM-35 and ZSM-5. Hence, this new high-silica zeolite offers
the opportunity to close the gap in the effective pore widths between ZSMJ and the twelve-
membered ring zeolite with the most restricted pore system, ZSM-12. This probably offers
new possibilities for shape selective catalysis in zeolites and molecular sieve separations.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge financial support by Deutsche Forschungsgemein-
schaft, Fonds der Chemischen Industrie and Max Buchner-Forschungsstiftung.
652
REFERENCES
1 J.L. Schlenker, J.B. Higgins and E.W. Valyocsik, in: J.C. Jansen, L. Moscou and M.F.M.
Post (Eds.), Zeolites for the Nineties; Recent Research Reports, 8th Intern. Zeolite
Conference, Amsterdam, July 10-14, 1989, pp. 287-288.
2 J.L. Schlenker, J.B. Hi ins and E.W. Valyocsik, Zeolites 10 (1990) 293-296.
3 R. Gramlich-Meier, Z%istallographie 177 (1986) 237-245
4 D.H. Olson, G.T. Kokotailo, S.L. Lawton and W.M. Meier,J. Phys. Chem. 85 (1981)
2238-2243.
5 E.W. Val ocsik and N.M. Page, Europ. Patent Appl. 174 121, Mar. 12, 1986, assigned to
Mobil OirCom.
6 J. Weitkamp, %’.Gerhardt and P.A. Jacobs, in: Proc. Intern. Symp. on Zeolite Catalysis,
Si6fok, Hungary, May 13-16, 1985, pp. 261-270.
7 J. Weitkamp, S. Ernst, P.A. Jacobs and H.G. Karge, Erdol, Kohle-Erdgas-Petrochem. 39
(1986) 13-18.
8 J.A. Martens, M. Tielen, P.A. Jacobs and J. Weitkamp; Zeolites 4 (1984) 98-107.
9 P.A. Jacobs and J.A. Martens, Synthesis of Hi h-Silica Aluminosilicate Zeolites, Elsevier
Science Publishers, Amsterdam, Oxford, New$ork, Tokyo, 1987, p. 8.
10 L.D. Rollmann and E.W. Valvocsik. Inoreanic Svnthesis 22 f 1982) 61-68.
11 Reference 9
12 K. Suzuki, $ . k ~ ~ ~ m mS. iShin,
, K. Fujisawa, H. Watanabe, K. Saito and K. Noguchi,
Zeolites 6 (19861 290-298.
13 G. Coudurier, C. Nacchache and J.C. Vedrine, J. Chem. SOC.,Chem. Commun. (1982)
1413-1415.
14 J.C. Jansen, F.J. van der Gaag and H. van Bekkum, Zeolites 4 (1984) 369-372.
15 E.M. Flanigen, in: J.A. Rabo (Ed.), Zeolite Chemistry and Catalysis; ACS Monograph
171, American Chemical Society, Washington, D.C., 1976, pp. 80-1 17.
16 H.G. Karge, J. Ladebeck, Z. Sarbak and K. Hatada, Zeolites 2 (1982) 94-102.
17 H.G. Karge, K. Hatada, Y. Zhang and R. Fiedorow, Zeolites 3 (1983) 13-21.
18 R.M. Dessau, US Patent 4 444 986, Apr. 24, 1984, assigned to Mobil Oil Corp.
19 P.A. Jacobs and J.A. Martens, in: Y. Murakami, A. Iijima and J.W. Ward (Eds.), New
Developments in Zeolite Science and Technology; Proc. 7th Intern. Zeolite Conference,
Kodansha/ Elsevier, Tokyo/Amsterdam, 1986, pp. 23-32.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 653
0 1991 Elsevier Science PublishersB.V., Amsterdam
NEW DATA ON THE STRUCTURE AND PROPERTIES OF ACIDIC SITES IN HZSM-5 ZEOLITES:
IR-SPECTROSCOPIC STUDIES AND NONEMPIRICAL QUANTUM CHEMICAL CALCULATIONS
SUMMARY
The quantum chemical analysis of the influence of geometry on properties of zeo-
lite acidic OH-groups and on the strength of the A1-0 bond in SiOAl bridges is
given. It is shown that bridge hydroxyls possessing high values of SiOAl angle
(-180O) are able to form a strained hydrogen bond with the neighboring lattice
oxygen atom attached to aluminum resulting in the appearance of HZSM-5 zeolites
.
of the broad absorption band at 3250-3300 cm-l in IR spectra The increase of
SiOAl angle in bridged hydroxyl and alkoxide leads to continuous weakening of
A1-0 bond. Therefore in the presence of basic molecules the A1-0 bond in the
straitened SiOAl bridges of alkoxides could be broken with the formation of tri-
gonal A1 cation coordinated with the base being a strong Lewis acid. Such unusu-
al manifestation of Lewis acidity of alkoxylated HZSM-5 zeolite is proved spect-
roscopically. The new hypothetical mechanism of the methanol conversion with the
participation of such Lewis acidic sites is proposed.
INTRODUCTION
Decationated ZSM-5 zeolites are active in the production of high quality ga-
soline from non-oil row materials (methanol, light olefins, paraffins etc). From
the scientific point of view they are convenient model objects for the study of
the influence of different structural factors on properties of their acidic si-
tes. Indeed the structure of the lattice and pores for these catalyst are well
established by X-ray analysis (ref.1). The high Si/Al ratio in HZSM-5 zeolites
provides rather homogeneous chemical surrounding of their active sites (ref.2).
Moreover among other zeolites they have a higher thermal stability and practi-
cally do not undergo dealumination during thermovacuum treatment.
The present report deals with the theoretical analysis of two novel phenomena
detected recently by ourselves using IR spectroscopy:
1. The existence in HZSM-5 zeolites of the considerable amount of acidic OH-
groups hydrogen bonded with the basic oxygen atom of the lattice (ref.3).
2. An unusual manifestation of Lewis acidity in the presence of adsorbed ba-
sic molecules for zeolites in which a fraction of OH-groups is substituted by
alkoxide fragments (ref.4).
In addition, on the basis of considered theoretical and experimental data the
new mechanisms of acid catalyzed reactions over HZSM-5 zeolites are discussed.
654
METHODS
IR spectra of powdered samples were measured in diffuse reflected light as
described in ref.5. Before study HZSM-5 zeolites (Si/Al = 17 and 351 were pre-
treated in vacuum for 2-3 h at 50OoC. The partial substitution of acidic OH-
groups of zeolites for alkoxide fragments was performed by chemisorption of
small quantities of propene on the zeolites at 300'K. MAS 13C NMR spectra were
measured using CXP-300 "Brucker" spectrometer.
Quantum chemical calculations were carried out using nonempirical SCF method
with a "Gaussian-80''program (ref.6). Five different basis sets ranged from mi-
**
nimal STO-3G to 6-31G were used (ref.71. Zeolite lattice was simulated by clu-
sters of following composition: H3A10HSiH3 (I), (OH)3A10HSi(OH)3 (11) and
OH(H)A1(OH)20Si(OH)ZOHAl~OH)3 (1111, (OH)3SiOSi(OH)20HA1(OH)3 (IY). Calculations
for cluster 11-IY were made only with STO-3G basis set. All calculations were
carried out with complete geometry optimization using gradient technique.
The literature data suggest that acidic OH-groups of HZSM-5 zeolites are non-
homogeneous (ref.8-9). Thus the substitution of only 20 % of acidic hydroxyls
for methoxide fragments by zeolite treatment with methanol vapor is accompanied
by the complete suppression of zeolite activity in ethylene oligomerisation
(ref.8). At the same time the remained 80 % of OH-groups are "free" as they are
still able to adsorbe benzene molecules with the larger kinetic diameter than
that of ethylene. The detailed analysis of the band shape in IR spectra of aci-
dic OH-groups perturbed by hydrogen bonding with adsorbed cyclohexane and benze-
ne molecules showed the existence at least of 5 types of hydroxyls with diffe-
rent acidic strength in HZSM-5 zeolites. It was also found (ref. 9 ) that poiso-
ning no more than 10 % of the sites (counted as lattice aluminum ions) was suf-
ficient to eliminate the activity of zeolites.
Quantum chemical interpretation of the broad IR band at 3250-3300 cm-' The typi-
cal spectrum of OH-groups measured at room temperature in diffuse reflected
light is shown in Fig.1. It consists of two narrow lines at 3740 and 3610 cm-l
corresponding to terminal silanols and isolated acidic hydroxyls respectively.
Additionally the broad absorption band with the maximum at 3250-3300 cm-l is
present. This band is always detected in the spectra of HZSM-5 zeolites but the
position of its maximum could be changed a little for the samples of different
origin.
The broad absorption band displays an unusual behavior. Under cooling of the
sample its maximum is shifted to higher wave numbers as in complexes with hydro-
gen bond. Adsorption of weakly basic molecules (C -C paraffins, CC1 , cyclohe-
655
xane, C02, etc) on zeolite leads to vanishing of both 3610 and 3250-3300 cm-l
bands and to the development of a single band at 3480-3530 cm-' characteristic
of acidic OH-groups forming H-complexes with these adsorbed molecules. The inte-
nsity of the broad 3250-3300 cm-l band in the IR spectrum measured at 500'C is
greatly reduced but can be completely restored after sample cooled to room tem-
perature. On the basis of these observations this band was assigned in ref.3 to
two different states of the same bridged hydroxyls such as isolated OH-groups
and those forming the strained hydrogen bond with the nearest basic oxygen atom
attached to aluminum.
, 3610
Fig.1.
IR diffuse reflectance
spectrum of HZSM-5 zeo-
lite (Si/A1=35) pretrea-
ted in vacuum at 70 K
for 4 h.
I I 1 I
Fig.2
Completely optimized
geometry of cluster I1
(LSiOA1 = 178O).
The main difference in the catalytic action of HZSM-5 and other zeolites is
usually explained by the higher protic acidity of the pentasil. Taking into
account that the acidic strength of the bridged hydroxyls should rise with the
increase of SiOAl angle we can assume that the hydroxyls characterized by the
broad 3250-3300 cm-l I R band would have the highest acidity. It is therefore
worthwhile to pay special attention to the analysis of broad I R bands of OH-
groups of high silica zeolites.
Lewis acidity of HZSM-5 zeolites The nature of Lewis acidic sites (L-sites) and
their role in catalysis by zeolites is widely discussed in the literature
(ref.12). Now the existence of several types of Lewis sites well established.
Among them there are the extralattice aluminum containing species and the latti-
ce trigonal aluminum or silicon cations appeared as a result of zeolite dehydro-
xylation at high pretreatment temperatures. In our opinion these sites, however,
could be considered as the active sites in the catalysis by zeolites with
caution. The reasons for this are as follows:
1. HZSM-5 zeolites hardly undergo dealumination during their activation under
conventional conditions and therefore the concentration of extralattice aluminum
is usually small. Moreover these sites are believed to participate in the coke
formation which is not characteristic of HZSM-5 zeolites.
2. The formation of lattice L-sites are known to proceed at temperatures abo-
ve 5OO0C (ref.12). So their appearance under usual activation conditions also
has a low probability. Moreover during catalytic reactions these L-sites could
be easily poisoned by moisture traces of the feedstock.
657
In this connection we would discuss the idea about two different ways of the
interaction between basic molecules and the acidic OH-groups in zeolites propo-
sed by Uytterhoeven et a1 in 1965 (ref.13). The first one is the usual reaction
of the base protonation:
H HB+
The second route is associated with the break of the Al”’0 bond in the Si-0-A1
bridge accompanied by the formation of complex between basic molecule and the
trigonal A1 cation being the strong Lewis acid:
H H
which is equal to the difference between total energy of the initial cluster and
/
the sum of total energies of 3i-OH and A ~ Kseparated fragments having equilib-
rium geometries.
The energies of complete A1-0 bond break for cluster I calculated with diffe-
rent basis sets are listed in Table 1.
TABLE 1
Basis set dependence of A1-0 bond energy (AE, kJ/mole) for cluster I
9
Basis set STO-3G 3-21G 6-31G MF’2/6-31G
9
According to the estimation at the MF’2/6-31G level the energy of Si-0 and 0-
H bonds breaking in the molecule H3SiOH which respectively correspond to enthal-
pies of reactions H3SiOH - H3SiO’ + H’ and H3SiOH - H3Si‘ + HO’ is approximately
the same and equal to 500-550 kJ/mole. Therefore the strength of the A1-0 bond
in the SiOAl bridge is much smaller than that of the Si-0 and 0-H bonds.
It is clear that minimal cluster model I is only a very primitive model of
the zeolite lattice. Therefore we also calculated the BE values of the A1-0 bond
in more extended clusters 11-IY. The transition from cluster I to I 1 is accompa-
nied by the decrease of the A1-0 bond energy from 176.5 to 136.5 kJ/mole. The
658
5 kJ/mole) due to formation of the intermolecular hydrogen bond between the hyd-
rogen atom of the methoxy group and the oxygen atom attached to aluminum.
The weakness of the Al-0 bond strength in high-silica zeolites could be mani-
fested in the course of chemical reactions as well as during interaction of the
acidic hydroxyls with adsorbed basic molecules. Let us demonstrate this using
the interaction of the bridged OH-group with the ammonia molecule as an example.
The nonempirical STO-3G calculations indicate that the interaction of ammonia
with the SiOAl bridge, which leads to the breaking of the A1-0 bond (scheme 2 )
proposed by Uytterhoeven is allowed energetically. Nevertheless the ammonia pro-
tonation (scheme 1) which in practice usually takes place is energetically more
favorable. There is, however, an opportunity to switch off the protonation chan-
nel by substitution of the acidic proton for an alkoxy fragment. As was mentio-
ned above such a substitution also results in weakening of the Al-0 bond. There-
fore the interaction of the NH3 molecule with the alkoxy group by the route
R R
0 0
>Si’ \AIL
\ + B -+ >Si’ B’.’Alf (4)
is even more probable.
659
I I I I I I I ,
-1 -1
2400 2300 u.cm 1700 1600 1500 v,cm
Fig.3. IR spectra of NH3 (A)and CD3CN (B) adsorbed on fresh HZSM-5 zeolite (1)
and on the sample with propene preliminary chemisorbed at 300 K (21. Line ( - -1
corresponds to the background.
The process of such an L-sites formation is a reversible one. They disappear
after removal of chemisorbed hydrocarbons by evacuation of the sample at higher
temperatures but are restored again after repeated chemisorption of the olefin.
It is worthwhile to emphasize that in this case no additional coordinatively un-
saturated L-sites was found from IR spectra of adsorbed weak basic molecules (H2
and CO). The conclusion was made that the formation of L-sites in the presence
of strongly basic molecules in zeolites Containing chemisorbed olefins proceeds
according scheme (4).where the oligomer hydrocarbon chains play a role of the
alkoxide R. The formation of alkoxy structures is evidenced by the appearance of
the intense line at 70 ppm corresponding t o resonance of C-atom in the fragment
'0-bH in MAS 13C NMR spectrum of chemisorbed 13C-enriched ethylene (Fig.4 ) .
/ I
The energy calculated for reaction (4) (B = NH3) indicates that this process
is energetically favorable: AE = 33.5 kJ/mole for cluster I (3-21C1 and AE = 13
660
kJ/mole for cluster I1 (STO-3G). For the acetonitrile molecule the energetics of
such reaction is less advantageous. It, however, became much more favorable f o r
bridged alkoxy groups with the larger SiOAl bond angle. Indeed, the increase of
this angle by 50' from its equilibrium meaning leads to essential enhancement of
system total energy and, as consequence, to sharp lowering the energy of A1-0
bond breaking in the presence of strong bases. At the same time for zeolites
with the low Si/A1 ratio the energy of the A1-0 bond is higher, than the energy
of the interaction between the basic molecule and the L-site. This explains why
L-sites are not formed in methoxylated zeolites of such type with strong basic
molecules adsorbed. 29
Fig.4.
MAS 13c NMR spectrum of
chemisorbed I3C en-
riched ethylene on
HZSM-5 at 370 K.
75 50 25 0
The next methanol molecule is able to break A1-0 bond and consequently to
661
transfer the bridge methoxide into the terminal one, as well as to dissociate on
the pair consisting of the formed trigonal A1 cation and the basic oxygen atom
attached to aluminum. This process could proceed via two energetically favorable
ways with the formation of either terminal A1-0 group and bridged methoxide or
A1-OCH3 fragment and bridged hydroxyl. The second structure is more preferable
in the presence of the methanol excess due to the formation o f the additional
strong hydrogen bond between the acidic OH-group and CH OH molecule.
3
In the first case the production of methane and formaldehyde could be accomp-
lished from the formed structure by the following synchronous mechanism (scheme
6 ) . It includes the attachment of the basic OH-group to bridge methoxide accom-
panied by hydride ion abstraction. The interaction of hydride ion with the nelg-
hboring terminal methoxide results in the break of the 0-C bond and formation of
the methane molecule. Simultaneously the restoration of initial SiOAl bridge and
the formation of an unstable bridged hydroxymethoxide group take place.
Abstraction of the proton from the latter complex being accompanied by the 0-C
bond breaking produces the formaldehyde molecule and regenerates the initial
acidic OH-group.
When second type structure is formed via CH30H dissociation on the A1-0 pair
the next adsorbed methanol molecule is activated by the acidic OH-group. Its
.further conversion could be presented by the scheme:
H
I
H3C'
662
The proton transfer from bridged hydroxyl to the adsorbed CH30H molecule is
accompanied by the nucleophylic attack of terminal methoxide by the protonated
methanol molecule. As a result the abstraction of hydrogen atom from terminal
methoxlde to neighboring oxygen and the formation of the acidic OH-group and
terminal ethoxide occur. In this case the regeneration of the initial SiOAl
bridge unit and acidic hydroxyl proceeds throughout the desorption of methanol
and ethylene molecules. The schemes similar to (6) and (7) could be also suggest
for dimethylether conversion.
The realization of scheme (7) would be accomplished only in the excess of
methanol. In the lack of the CH OH molecule the structure containing the A1-OCH
3 3
group and acidic OH-group would be isomerized into a more energetically prefe-
rable one, which leads to methane and formaldehyde formation. It is worthwhile
to mention that the schemes presented here allow to explain the difference
observed in the products of methanol conversion at low (methane and formaldehy-
de) and high (hydrocarbons) pressures of alcohol (ref.161.
REFERENCES
K.J.Chao, J.C.Lin, Y.Wang, G.H.Lee, Single crystal structure refinement of
TPA ZSM-5 zeolites, Zeolites 6(1) (1986)pp. 35-38.
V.B.Kazansky, Theory of Broensted acidity of crystalline and amorphous
aluminosllicates: quantum chemical cluster model and IR spectra Kinet.
Catal. 23(6) (1982) pp.1334-1348.
V.L.Zholobenko, L.M.Kustov, V.Yu.Borovkov, V.B.Kazansky. A new type of
acidic hydroxyl groups in ZSM-5 zeolite and in mordenite according to
diffuse reflectance i.r. spectroscopy, Zeolites 8 ( 5 ) (1988)175-178.
A.S.Medin, V.Yu.Borovkov. V.B.Kazansky, A.G.Pelmenshchikov,G.M.Zhidomirov,
On the unusual mechanism of Lewis acidity manifestation in HZSM-5 zeolites,
Zeolites 1990 (in press)
V.B.Kazansky, Diffuse reflectance IR spectroscopy and its new potentialities
in studying chemisorbed species and the structure of surface oxide
catalysts, Izv. AN SSSR 1 (1984) pp.40-51.
J.S.Binkley, R.A.Whiteside,R.Krishnan, R.Seeger, D.J.DeFrees. H.B.Schlege1,
S.Topio1, L.R.Kahn, J.A.Pople, QCPE, 13 (1981) 507.
W.J.Hehre, L.Radom. P.v.R.Schleyer, J.A.Pople, Ab initio molecular orbital
theory, Willey Intersci., New York etc., 1986.
A.S.Medin, Ph.Diss., Moscow, 1990.
E.A.Lombardo. G.A.Si11.W.K.Hal1. The assav of acid site on zeolites as
measured by ammonia poisoning, J. Catal., 119(2) 1989 pp.426-40.
10 J.L.Schlenker, J.J.Pluth, J.V.Smith,Position of cations and molecules in
zeolites with the mordenite framework. IX. Dehydrated H-mordenite via acid
exchange, Mat. Res. Bull., 14(7) (1979)pp.849-56.
11 I.N.Senchenya, V.B.Kazansky, S.Beran, Quantum chemical study of the effect
of the structural characteristics of zeolites on the properties of their
bridging OH groups, J. Phys. Chem., 90(20) (19861 4857-4859.
12 V.B.Kazansky, On the nature of Lewis acidic sites in high silica zeolites
and the mechanism of their dehydroxylation, Catalysis Today,3 (1988) 367-72.
13 L.B.Uytterhoeven, L.G.Crystner,W.K.Hal1, Studies of the hydrogen held by
solids, J. Phys. Chem., 69(6) (1965) pp.2117-2126.
14 L.Kubelkowa, J.Novakova, P.Jiru, Reaction of small amounts of methanol on
HEM-5, HY and modified Y zeolites, In: Structure and Reactivity of
Modified Zeolites, Stud. Surf. Sci. Catal. 18 (1984) pp.217-224.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 663
01991 Elsevier Science Publishers B.V., Amsterdam
ABSTRACT
Activation of powdered, undiluted zeolites was studied in-situ
by FTIR diffuse reflectance (DRIFT) spectroscopy. From the DRIFT
spectra we constructed contour plots, which display the process
quasi continuously.
At temperatures below 2OO0C, the diffusion of water and
ammonia towards the cation coordination sphere is seen.
The maximum loss of a particular NH species was observed at
500°C. The concentration of OH species increases most strongly at
430"C, after the on-set of an almost uniform decomposition of all
NH species. The activation of 0.93 NH,' erionite was completed at
around 600°C.
INTRODUCTION
Diffuse Reflectance Infrared Fourier-Transform (DRIFT-)
spectroscopy has a high potential for in-situ studies of
heterogeneous catalytic systems. Even very slow processes can be
monitored over long periods (ref. 1). Most samples may be
investigated without further pretreatment in a wide range of
temperatures and pressures (ref. 2). Lateral resolution in the
millimeter range can be achieved.
We used DRIFT spectroscopy to investigate the activation
process of zeolites i n - s i t u under atmospheric pressure between room
temperature and 640°C. NH,' exchanged erionites were selected as
test compounds. The DRIFT results were compared to the results of
a thorough study of erionites by conventional infrared transmission
technique (ref. 3).
Here we describe the experimental technique and present the
first results.
664
SAMPLING SYSTEM
DRIFT spectra are given in Kubelka-Munk units f (R) (ref. 4 ) ,
which are directly related to the absorbance coefficient k of the
sample and its scattering coefficient s via
f(R) = (1 - R/R')' / 2R/R' = k / S . ( 1 )
R is the single-beam reflectance spectrum of the sample, R' the
single-beam reflectance spectrum of a non-absorbing standard.
The Kubelka-Munk equation (1) was derived for the ideal case
of purely diffuse reflectance. For real samples, diffuse
reflectance is always accompanied by specular reflectance, which
upsets the ordinate scale and deteriorates the detection limits.
The only way to prevent contributions of specular reflectance from
reaching the detector is to select a DRIFT attachment of a
particular optical design, the so-called off-axis geometry
(ref. 5), where the incoming beam and the normal to the sample
surface do not share a common plane (or axis) with the reflected
beam (Fig. 1).
A heatable sample stage for DRIFT spectroscopy, which is
commercially available (HVC-DRP chamber of Harrick Scientific
Corp., Ossining/NY), was tested over a wide temperature range. The
vacuum chamber body, which encloses the sample stage, was omitted
because the investigation was carried out at ambient pressure. Any
change in the sample position during the measurement series,
including realignment, was avoided.
reflected beam
incoming beam
sample
to power supply
heater
thermal insulator
adjustment screw
base
S i n g l e beam s p e c t r a of t h e t e s t sample ( c o r r e s p o n d i n g t o R i n
e q n . 1) a r e summarized i n F i g . 2 . The a r e a below a p a r t i c u l a r c u r v e
r e f e r s t o t h e t o t a l amount of modulated r a d i a t i o n r e a c h i n g t h e
d e t e c t o r . Upon h e a t i n g t h e HVC-DFW sample s t a g e , t h e s i n g l e beam
s p e c t r a become i n c r e a s i n g l y f l a t ( F i g . 2 a ) . The observed r e d u c t i o n
i n e n e r g y t h r o u g h p u t i s more s e v e r e a t s h o r t e r w a v e l e n g t h s (compare
the lowering of t h e c u r v e maxima at 4 0 0 0 a n d 2200 cm-I). This
s u g g e s t s a g e o m e t r i c a l e f f e c t dominating t h e energy d r o p d u r i n g
h e a t i n g , p r o b a b l y b e due t o t h e r e l a t i v e l y l o n g h e a t i n g zone of t h e
HVC-DRP sample s t a g e , c h a n g i n g t h e sample p o s i t i o n r e l a t i v e t o t h e
reflectance mirrors.
1 1
/p
25 *C a)
i 0,5 I
~
i 0.
,
0 0
6000 4000 2000 0 6000 4000 2000
+- cm-' +- cm-'
F i g . 2 . S i n g l e beam s p e c t r a of 0 . 9 3 NH,' e r i o n i t e a t d i f f e r e n t
t e m p e r a t u r e s . a ) Sample s t a g e of HVC-DRP chamber. b ) Oven a s i n
F i g . 1.
The o b s e r v e d e n e r g y l o s s d u r i n g h e a t i n g r e d u c e s t h e S / N r a t i o ,
causes background fluctuations in the spectra and introduces
ordinate non linearities. These effects can be reduced
c o n s i d e r a b l y , when t h e r e f e r e n c e s p e c t r u m i s measured a t t h e same
t e m p e r a t u r e a s t h e sample spectrum.
The b e s t results c o u l d be observed using a sample stage
according t o Fig. 1, whose t h e r m a l e x p a n s i o n was minimized by
i n t r o d u c i n g t h e h e a t e r d i r e c t l y i n t o t h e sample b u l k ( F i g . 2 b ) .
666
EXPERIMENTAL
A Bruker FTIR spectrometer IFS 88 was used for all tests of
the heatable sample stage of the HVC-DRP reaction chamber. The
sample stage was inserted into a diffuse reflectance attachment
D R A 3 (Harrick Scientific Corp. , Ossining/NY, USA) .
All the other FTIR spectra were scanned on an IRF 180 (ZWG,
Akademie der Wissenschaften der DDR, Berlin), equipped with a the
off-axis diffuse reflectance attachment of the same manufacturer.
128 interferograms were co-added before Fourier transformation.
The thermal insulator of the heatable sample stage was made of
glass ceramics (Fig. 1). A micro thermocouple was used for
temperature measurement. The alignment of the thermocouple to the
uppermost layer of the powder is important for exact measurement.
Samples were heated by 2 K min-', and during the spectral
measurements the temperature was kept constant.
The synthesis and ion exchange of the erionites used in this
study have already been described (ref. 3). The samples were
investigated as received. Finely ground KBr was used as reference.
No features, e.g. peaks due to atmospheric C02, have been omitted
from the spectra.
A s a first step,
all the constant
(background) features
apparent during
heating are removed by
s u b t r a c t i n g
consecutive spectra.
It depends upon the
available software,
w h e t h e r t h e
temperature intervals
have to be constant or
not. A high S/N ratio
and a constant
ordinate accuracy in
the single beam
s p e c t r a a r e
prerequisites.
The ordinate
accuracy of DRIFT
spectra is mainly
determined by the
scattering coefficient
s in eqn. 1. It varies
remarkably for
Fig. 3. DRIFT spectra of 0.93 NH,' different sample
erionite during activation at the open preparations, even for
atmosphere.
samples from the same
batch. One must only
evaluate spectra, which belong to one consecutive series of
measurements.
The D R I F T difference spectra in Fig. 4 enhance all the changes
taking place during activation, which have been discussed regarding
Fig. 3. The removal of all the constant features did not simplify
the shapes significantly.
In the following, we shall regard the complete set of curves
in Fig. 4 as a landscape. The height of the hills corresponds to
the increase of a particular XH species per temperature step, the
668
d e e p n e s s of t h e v a l l e y s t o t h e d e c r e a s e i n c o n c e n t r a t i o n . A t e v e r y
v i e w i n g a n g l e mountains i n t h e f o r e g r o u n d h i d e f e a t u r e s b e h i n d ,
whereas a map, t h e s o - c a l l e d c o n t o u r d i a g r a m , p r o v i d e s immediate
a c c e s s t o a l l t h e d e t a i l s of t h e measured s e r i e s .
Contour d i a g r a m s f o r t h e DRIFT d i f f e r e n c e s p e c t r a i n F i g . 4
a r e g i v e n i n F i g s . 5 and 6 . To e n s u r e c l e a r n e s s of t h e monochrome
d i s p l a y , t h e r e g i o n s of n e g a t i v e r e f l e c t a n c e c h a n g e s ( d e c r e a s i n g
c o n c e n t r a t i o n s ) d u r i n g h e a t i n g a r e h i g h l i g h t e d i n F i g . 5, r e g i o n s
of p o s i t i v e r e f l e c t a n c e c h a n g e s ( c o r r e s p o n d i n g t o i n c r e a s i n g
concentrations) i n Fig. 6 .
A t t e m p e r a t u r e s below 200°C t h e I R r e f l e c t a n c e d e c r e a s e s i n
t h e r e g i o n 3700 - 2800 cm-’ due t o d e s o r p t i o n o f w a t e r and ammonia
( F i g . 5 ) . The r e f l e c t a n c e l o s s e s s t a r t most pronounced around
3450 cm-’ (OH s p e c i e s ) and 3 1 0 0 cm-’ ( N H s p e c i e s ) . Above 150°C t h r e e
bands f o r d e s o r b i n g NH c a n be s e e n ( 3 3 0 0 , below 3100, below
2900 cm-I).
Up t o 200°C a s i m u l t a n e o u s i n c r e a s e i n r e f l e c t a n c e i s o b s e r v e d
between 2800 and 2200 cm-’. The i n c r e a s e d r e f l e c t a n c e i s e a s i l y s e e n
669
640
O C
530
420
310
200
130
640
O C
530
420
310
200
130
Cm-'
ACKNOWLEDGEMENT
This research was supported by The Norwegian Research Council
for Science and the Humanities (NAVF).
REFERENCES
1 R. Salzer, K.-H. Ste nberg, P. Klaeboe, B. Schrader, Zeolites
submitted.
2 S. A. Johnson, R.-M Rimkus, T. C. Diebold and V. A. Maroni
Appl. Spectr. 42 1 9 8 8 ) 1 3 6 9
3 A. Kogelbauer, J. A . Lercher, K.-H. Steinberg, F. Roessner,
A. Soellner and R V. Dmitriev: Zeolites 9 ( 1 9 8 9 ) 2 2 4 .
4 P. Kubelka and F. Munk: 2. Techn. Phys. 1 2 ( 1 9 3 1 ) 5 9 3 .
5 D. M. Hembree and H. R. Smyrl: Appl. Spectr. 4 3 ( 1 9 8 9 ) 2 6 7
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 671
0 1991 Elsevier Science Publishers B.V., Amsterdam
ABSTRACT
The IR band at 960 cm'l observed on TS is due to a local
stretching mode of a [Ti04] unit in the silicalite framework.
Framework Ti does not show Lewis acidity as probed by CO adsorp-
tion at 77 K. TiOH and SiOH have undistinguishable IR properties.
At 77 K they form with CO very weak 1:l OH...CO adducts. Small
amount of extralattice Ti in form of Ti02 can be probed by CO
adsorption at 77 K.
INTRODUCTION
The substitution of Ti and A1 for Si in zeolites of the penta-
sil family (Silicalite) leads to Ti-Silicalite and ZSMS which are
two important catalysts for oxidation with HZOZ (refs. 1-3) and
acid catalyzed reactions (ref. 4 ) .
The characterization of Titanium-Silicalite (TS) by means of
physical methods has been recently published (ref. 5). However, a
few problems are still open concerning: i) the presence of extra-
lattice Ti (as Ti02 microparticles); ii) the interpretation of
the vibrational spectrum of the solid; iii) the crystallinity of
TS with respect to pure S and ZSMS; iv) the presence of titanols
in the channel8 and cavities.
The CO molecule is an efficient probe of Lewis and Broensted
acidity and can be used to explore the acidity of OH groups in
the channels (TiOH and SiOH in TS, (Si,Al)OH, SiOH and AlOH in
H-ZSM5). On dehydroxylated samples coordinatively unsaturated
Ti4+ and A13+ ions in lattice and extralattice positions can be
revealed as well, because they can form Lewis adducts with CO.
In this contribution we report on the IR spectra of CO ad-
sorbed at 77 K on TS, s and ZSMS. The vibrational spectra of s,
TS and Na-ZSM5 are also compared and discussed.
EXPERIMENTAL
Silicalite and Titanium-Silicalite have been synthesized in
Montedipe laboratories following the method described in ref. 2;
Na-ZSM5 and H-ZSM5 (external surface area 60 m’9-l) have been
provided by the same laboratory. The ER spectra have been ob-
tained on a Bruker IFS 113V FTIR spectrometer using a specially
designed silica cell permanently attached to a vacuum manifold
and allowing in situ outgassing procedures at temperatures in the
273-1073 K interval and gas dosing at 7 7 K. The samples were
either in form of thin pellets or of films deposited on KBr or Si
plates.
0.5 F'LI
A / I
1
I0
YRVENUHBER C H - I
Silicalite
The IR spectrum in the OH stretching region (Fig.2a) is char-
acterized by two main absorptions at 3750-3700 cm-' (composit
a
t
a 2
Titanium-Silicalite
An identical experiment carried out on TS outgassed at 573 K
gives the spectra reported in Fig.3a and 3b (OH and CO stretching
region respectively). The great similarity with the spectra of
Fig.2 is immediately evident. This observation has two main
consequences: i) titanols (either on framework or extra-framework
Ti) cannot be easily distinguished from silanols by IR spectros-
copy (especially when the Titanium content is small) and ii)
titanols (either framework or extraframework) have Broensted
acidity not substantially different from silanols. In conclusion,
the presence of Ti does not substantially modify the OH distribu-
tion and their acidity. In these conditions we can ask wether
TiOH groups are really present (specially if we consider that if
Ti is totally framework and if the Ti-0-Si bridges are not at
least partially hydrolyzed TiOH should be absent). For the time
being we cannot answer this question. However, we shall come back
again on this problem later on, on the basis of further data.
As known from indipendent experiments on the Ti02/C0 system
(ref. 12) , the adsorption of CO on microparticles of Ti02 out-
gassed at temperature t 873 K, gives surface Ti4+cus-C0 (cus:
coordinatively unsaturated) species characterized by a well
defined high intensity peak at 2179 cm-'. The presence, or the
absence, of this peak on properly outgassed TS samples can be so
used as a text of the presence or the absence of extraframework
Ti in form of Ti02 microparticles. The results of this experi-
ments on a TS sample outgassed in vacuo at 873 K are reported in
Fig.4a and 4b. In the same figure the spectrum of CO (CO-stretch-
678
1 n b
t
a TO' Ii1 0.5
-z
r
0
Y
u
z
U
m
w
0
VI
m
U
a
I!
h
'
absence of TiOH groups. First of all we can now say with confi-
dence that TioH or Ti02 microparticles do not play any relevant
role in the spectrum of TS (OH stretching region), and secondly
that TioH (if present) must comes only from partial hydrolysis of
polar Si-0-Ti bridges, as already hypothesized in ref. 5. In
order to prove or reject the hypothesis that Si-0-Ti bridges
exposed in the channels and cavities are preferential sites for
H20 adsorption, the following comparative experiment has been
designed. Silicalite and Ti-Silicalite samples were outgassed at
973 K in high vacuum for 4 hrs to eliminate all the hydrogen
bonded hydroxyl groups. After this treatment the IR spectra in
the OH stretching region were substantially undistinguishable
(with only one peak left at 3720 cm-' similar to that shown in
Fig.4a). H20 vapuor was then dosed (10 torr) on the sample and
680
CONCLUSIONS
The IR band observed in the spectrum of TS at 960 cm-', asso-
ciated with framework Ti, is due to a local impurity stretching
mode of the [Ti04] unit in the Silicalite lattice. The small
fraction of extralattice Ti in form of Tio2 microparticles does
not contribute to the IR spectrum of TS. TiOH and SiOH cannot be
distinguished by IR spectroscopy and have very similar acidity
(as tested by CO adsorption at 77 K). Moreover, comparison with
the spectra of OH...CO adducts on H-ZSM5 shows that their acidity
is much lower. Lewis acidity associated with Ti4+ ions is also
pratically absent even on samples outgassed at 973 K.
REFERENCE8
W. Holderich, M. Messe and F. Naumann, Angew. Chem. Int. Ed.
Engl., 27 (1988) 26.
C. Neri, A. Esposito, B. Anfossi and F. Buonomo, Eur. Pat.
100 119.
C. Neri, M. Taramasso and F. Buonomo, U.K. Pat. 102 665.
J.A. Rabo, Catal. Rev. Sci. Technol., 24 (1982) 202.
M.R. Boccuti, K.M. Rao, A. Zecchina, G. Leofanti and G. Petri-
nil Spectroscopic characterization of Silicalite and
Titanium-Silicalite, in: C. Morterra, A. Zecchina and G.
Costa (Eds.), Structure and Reactivity of Surfaces, Elsevier,
Amsterdam, 1989, pp. 133-144.
P. Comba and A . Merbach, Inorg. Chem., 26 (1987) 1325.
A. Miecznikowski and J. Hamuza, Zeolites, 7 (1987) 249.
M.F. Best and R.A. Condrate, J. Mat. Sci. Letters, 4 (1985)
994.
B.G. Varshal, V.N. Denisov, B.N. Maurin, G . A . Paulova, V.B.
Podobedov and K.E. Stebin, Opt. Spectrosc. (USSR), 47 (1979)
344.
10 G.C. Pimentel and A.L. McClellan, The hydrogen bond, W.H.
Freeman and Co., San Francisco and London, 1960.
11 V.B. Kazanskii, Kinet. Catal., 28 (1987) 482.
12 G. Spoto, C. Morterra, L. Marchese, L. Orio and A. Zecchina,
Vacuum, in press.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 681
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
The p r o p e r t i e s of Bog u n i t s and a c i d p r o p e r t i e s of boralites
w i t h v a r i o u s boron c o n t e n t s w e r e s t u d i e d b y I R s p e c t r o s c o p y . The
band of a n t i s y m m e t r i c s t r e t c h i n g v i b r a t i o n s of 9-0 i s s p l i t i n t o
t w o m a x i m a . I t s e e m s t o b e d u e t o t h e removal of d e g e n e r a t i o n of
t h i s vibration. The i n t e n s i t y of t h e B03 doublet increases
l i n e a r l y w i t h t h e b o r o n c o n t e n t b o t h i n N a - and H - b o r a l i t e s . The
e x t i n c t i o n c o e f f i c i e n t of 9-0 v i b r a t i o n i s d i s t i n c t l y l h i g h e r i n
t h e . . c a s e of H-boralites. The c o n c e n t r a t i o n of 3720 c m hydroxyls
CBronsted a c i d s i t e s 3 i n c r e a s e s l i n e a r l y w i t h b o r o n c o n t e n t i n
H - b o r a l i t e s and i s close t o t h e t h e o r e t i c a l v a l u e s . S m a l l amounts
of L e w i s a c i d sites a r e p r e s e n t i n H-boralites. their acid
s t r e n g t h b e i n g h i g h e r t h a n i n HZSM-5.
I NTRODUCTI ON
Isomorphically substituted zeolites have recently been
studied extensively because of their interesting chenucal
p r o p e r t i e s and p o t e n t i a l i n d u s t r i a l a p p l i c a t i o n [ f o r a r e v i e w see
ref. C1>1. Boron s u b s t i t u t e d z e o l i t e s . boralites, which owing t o
the small s i z e of boron atom show properties not observed in
zeolites. draw the greatest attention. The boron atom is
t r i -coordinated i n d e h y d r a t e d b o r a l i tes , t h e B03 band a p p e a r s i n
t h e spectrum Cref. 2.31. The p r o p e r t i e s of B03 units i n boralites
of v a r i o u s b o r o n c o n t e n t s w e r e s t u d i e d b y I R s p e c t r o s c o p y a n d t h e
r e s u l t s a r e described i n t h e present paper.
Our p r e v i o u s I R s t u d y C r e f . 3,4> h a s shown t h a t f o u r k i n d s of
-1
OH g r o u p s exist i n H - b o r a l i t e s . Only 3720 cm h y d r o x y l s were
f o u n d t o b e B r z n s t e d a c i d sites. Their acid strength is much
lower than in zeolites Cref. 2-51. The concentration of the
B r z n s t e d a c i d s i t e s i n H-boralites of v a r i o u s boron c o n t e n t s w a s
s t u d i e d by I R s p e c t r o s c o p y and t h e r e s u l t s a r e a l s o presented i n
t h i s paper.
682
EXPERIMENTAL
Five samples of MFI boralites were synthesized in the
N a 0-TPABr-B 0 -SiO -H 0 s y s t e m as d e s c r i b e d i n d e t a i l i n r e f . 7 .
2 2 3 2 2
C o n c e n t r a t e d s i l i c a sol, s o l i d o r t h o b o r i c a c i d H3B03. sodium
hydroxide, and distilled water were used as substrates and
tetrepropylammonium bromide TPBABr as a template substance.
Individual synthesis differed only in the molar ratio n
RM
C=Si02/B203 in the reaction mixture). which was varied in the
r a n g e 5-100. C r y s t a l l i z a t i o n w a s c a r r i e d o u t i n steel autoclaves
lined with PTFE. at 438 K. for 7 days, without stirring. The
p r e c i p i t a t e w a s washed w i t h d i s t i l l e d w a t e r a n d d r i e d i n air. In
o r d e r t o decompose o r g a n i c species boralites were c a l c i n a t e d i n
a i r a t 773 K i n a t h i n l a y e r C l - 2 mml. for 4 h. Boralites thus
p r e p a r e d are d e n o t e d as Na-boralites. They w e r e n e x t t r a n s f o r m e d
into the NH4-form by triple ion exchange in ammonium chloride
solution at room temperature. The compositions of Na- and
NH - b o r a l i t e s ( o b t a i n e d from chemical analysis) are presented in
4
T a b l e 1.
XRD studies have shown that all the samples were highly
crystalline without crystalline admixtures. They had the
or thor hombi c MFI s t r u c t u r 8 .
The N a / N H 4 ion exchange resulted in some boron loss from
boralites. This problem is d i s c u s s e d i n detail i n our previous
paper Cref. 81. The c a l c i n a t i o n of NH - b o r a l i t e s r e s u l t s i n a
4
further boron loss Cref. 8). The b o r o n c o n t e n t s i n H-BOR-8.
H-BOR-5. H-BOR-4. H-BOR-3. H-BOR-2 w e r e f o u n d t o be 0.88, 0.59,
0.69. 0.85 a n d 1 . 0 5 B/u. c. r e s p . upon c a l c i n a t i o n i n a i r a t 773 K .
for 4 h C s a m p l e numbers a r e t h e s a m e as i n o u r p r e v i o u s p a p e r ,
ref. 71.
For I R s t u d i e s NH - b o r a l i t e s were p r e s s e d into thin wafers
4
C4-7 m g cm-'). The w a f e r s w e r e activated in situ i n I R c e l l in
vacuum at. 773 K , for 1 h. It was assumed that the boron loss
during this activation was the same as during the calcination
u n d e r c o n d i t i o n s described i n r e f . 8.
T h e s p e c t r a w e r e r e c o r d e d u s i n g a SPECORD 75 I R s p e c t r o m e t e r
CCarl Zeiss J e n a l working on l i n e w i t h a K S R 4100 minicomputer.
Pyr i d i ne C PCCh-G1 i w i c e l u s e d w a s o f a n a l y t i c a l g r a d e .
683
TABLE 1
Compositions of N a - and NH -boralites
4
Sample
* composition
~~ ~~
Na-BOR-8
30H0.10CCB02’0.
3OcAlo2’0. 1OcSi02’Q5. 6’
NH4 -BOR-8
03CNH4’0.37ccB02’0.2QcA102’0. 1lcsi02’S5. 6’
Na-BOR-5 80CCB02’0.
8OcSi02’Q5. 2’
NH 4 -BOR-5
04CNH4’0.69[cB02’0. 63CA102’0.10csi02395.2’
N a -BOR -4
N a lOO[CBo2’l.
. 0OcSi02’Q5. 0’
NH4-BOR-4
Na0..02CNH4’0. 84CCB02’0. 78cA10220.0ScSi02’Q5. 0’
N a -BOR -3 N a l30H0.
. 4OCSio2’Q4.
10CcB0231. 6’
NH4-BOR-3
01CNH4’0.98[cB02’0. 99csi022Q4. 63
Na-BOR-2 N a l60H1.
, 0OCCB02’2. 6OcSi02’Q3. 4’
NH4-BOR-2 OlCNH4’1. 36[cB02’1. 37csi022Q3.4’
* s a m p l e numbers a r e t h e same a s i n p r e v i o u s p a p e r C r e f . 73
o x y g e n i n 0 B---.O u n i t s . A n o t h e r i n t e r p r e t a t i o n a s s u m e s t h e removal
3
o f d e g e n e r a t i o n o f t h e v3 €3-0 v i b r a t i o n i n B03 u n i t s . This c o u l d
be d u e t o t h e f a c t t h a t B03 u n i t s a r e n o t i s o l a t e d b u t e a c h o x y g e n
i s bonded t o a s i l i c o n a t o m of t h e lattice. I t s h o u l d be n o t e d
that the v3 vibration band in the spectra of many crystalline
i n o r g a n i c b o r a t e s i s a l s o s p l i t C r e f . 91.
In order to get more information on the origin of the
s p l i t t i n g , t h e s p e c t r a of Na- a n d H-boralites w i t h v a r i o u s boron
c o n t e n t s C a c t i v a t e d a t 773 KI w e r e r e c o r d e d . I t w a s supposed t h a t
if t w o k i n d s o f b o r o n sites d i f f e r i n g i n B-0 force c o n s t a t e x i s t
in the boralite lattice. one of them should be occupied
p r e f e r e n t i a l l y a t l o w boron c o n t e n t s . I n t h i s case, the intensity
r a t i o of b o t h m a x i m a 1380 a n d 1 4 0 5 c m - l should change w i t h boron
content. On t h e o t h e r h a n d i f t h e s p l i t t i n g t h e v 3 b a n d w a s d u e t o
t h e d e g e n e r a t i o n removal, t h e i n t e n s i t y r a t i o is expected n o t to
depend on boron c o n t e n t . The s p e c t r a of H-boral i tes c o n t a i n i n g :
0.28, 0.59, 0 . 6 9 and 1 . 0 5 B/u. c . are presented i n Fig. 1. The
i n t e n s i t y r a t i o of 1380 a n d 1 4 0 5 c m - l bands p r a c t i c a l l y does n o t
depend on b o r o n c o n t e n t . T h e s a m e w a s a l s o o b s e r v e d i n t h e case of
Na-boralites. It suggests that the degeneration removal is the
reason f o r t h e s p l i t t i n g of t h e v3 b a n d o f €3-0 s t r e t c h i n g i n B03
units. Of course t h e possibility that t w o kinds of boron sites
d i f f e r i n g i n B-0 f o r c e c o n s t a n t but without preference i n their
o c c u p a t i o n c a n n o t b e t o t a l 1y e x c l u d e d .
Fig. 2 shows the plots of intensities of 1380, 1405 cm-l
d o u b l e t as a f u n c t i o n of boron c o n t e n t i n N a - a n d H-boralites. In
t h e case o f H-boralites. t h e loss of boron d u r i n g t h e a c t i v a t i o n
o f NH -form w a s t a k e n i n t o a c c o u n t . B o t h p l o t s a r e l i n e a r . I n t h e
4
case of H - b o r a l i t e s t h e s l o p e i s much h i g h e r t h a n i n N a - b o r a l i t e s .
M o s t probably t h i s is due t o t h e higher e x t i n c t i o n c o e f f i c i e n t of
t h e v3 B - 0 s t r e t c h i n g Cand h e n c e t o h i g h e r 8-0 bond p o l a r i z a t i o n > .
We can however not exclude a possibility that some B atoms i n
Na-boralites are n o t i n B03 units and i t could r e s u l t in a low
i n t e n s i t y o f t h e B 0 3 band.
Our p r e v i o u s s t u d y C r e f . 101 h a s shown t h a t t h e i n c r e a s e i n
boron content results in the contraction of the unit cell of
b o r a l i t e s ( b o r o n i s s m a l l e r t h a n s i l i c o n > . T h e force c o n s t a n t s o f
Si-0 s t r e t c h i n g i n boralites w e r e f o u n d t o be i n d e p e n d e n t of B
content. T h i s l a s t e f f e c t i s d i s c u s s e d i n t e r m s of t h e c o l l e c t i v e
685
7 -
c
I
er, 5 -
\
E
\
In
0 3 -
2
0
(0
. -
$ 1
a
1 2 3
D I U.C.
-P/ theoret.
.-
0
U
Cl
0
a
c
v)
C
:0
115; -,, Lewis-
L
1.o
(B+Al-Na)/u.C.
F i g . 3. - The c o n c e n t r a t i o n s of Brgnsted a c i d sites COD,
t h e o r e t i c a l values of c o n c e n t r a t i o n of Brgnsted sites Co> and t h e
i n t e n s i t y of PyL band i n H - B o r a l i t e s a s a f u n c t i o n of boron
c o n t e n t Co3
model of zeolites Cthe electronegativities of Si and B are
practically the same>.
REFERENCES
1 M. T i e l e n . M. G a l l e n a n d P. A. J a c o b s , P r o c . I n t . Symp. Z e o l i t e
C a t a l y s i s , , S i o f o k , Hungary, May 1985. p. 1.
2 G. C o u d u r i e r , J . C. V e d r i n e . P u r e Apl. Chem. , 58. C1986>, 1389.
3 J. D a t k a and Z . Piwowarska. J . Chem. Soc. , F a r a d a y T r a n s . I ,
85, C1989>, 47.
4 J . D a t k a and Z. Piwowarska. J . Chem. Soc., F a r a d a y T r a n s . I .
85, C19893, 837.
5 K. F.M.G. J . S c h o l l e . A.P.M. Kentgens. W . S . Veeman, P. F r e n k e n
a n d G. P. M. van d e r Velden. J . Phys. Chem. , 88. C19843, 5.
6 P. Ratnasamy, S.G. Hegde a n d A. J . Chandwalkar, J . C a t a l . , 102,
1986. 467.
7 A. C i c h o c k i , M. M i c h a l i k , M. Buf a n d J . P a r a s i e w i c z -
Kaczmarska, Zeolites. 10. (19893. i n p r i n t .
8 A. C i c h o c k i . M. M i c h a l i k . M. BUS. W. Lasocha a n d Z. Saw&owicz,
Zeolites. 10. Cl989>, i n p r i n t .
9 C.W. Weir and R . A . S c h r o e d e r . J o u r n a l of R e s e a r c h of t h e
N a t i o n a l Bureau of S t a n d a r d s A. 6 8 A C 5 > , 465. 1964.
10 A. Cichocki. J. Datka, M. M i c h a l i k . A. O l e c h , a n d
Z . Piwowarska. J . Chem. Soc., F a r a d a y T r a n s a c t i o n s 1 . 86C4).
c19903. 753.
I1 J . Datka and E. TuPnik, J . C a t a l . , 102. C19863. 43.
12 J . W . Ward, J. C a t a l . , 10. C19681, 34.
13 J . W. Ward, J . C o l l . I n t e r f a c e Ski. , 28, ClQ683. 269.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 689
0 1991 Elsevier Science Publishers B.V., Amsterdam
SUMMARY
INTRODUCTION
The i n t e r a c t i o n o f aromatic molecules w i t h t h e h y d r o x y l groups o f
z e o l i t e s r e s u l t s i n a decreased frequency and an i n c r e a s e d i n t e n s i t y f o r
t h e h y d r o x y l i n f r a r e d band. The e x t e n t o f p e r t u r b a t i o n o f t h e h y d r o x y l
band i s o f t e n r e l a t e d t o t h e a c i d s t r e n g t h (1,21.
I n t h i s s t u d y a s e r i e s o f aromatic molecules i . e . benzene, t o l u e n e ,
o-xylene, p-xylene, m-xylene and cumene a r e absorbed on a 100% exchanged
HY sample and t h e i r e f f e c t on t h e h i g h f r e q u e n c y ( h . f . ) h y d r o x y l group i s
monitored. Both t h e decrease i n frequency and i n c r e a s e d i n t e n s i t y o f t h e
h.f. band a r e m o n i t o r e d and an e l e c t r o s t a t i c model, due o r i g i n a l l y t o
Coggeshall ( 3 1 , i s u t i l i s e d t o p r e d i c t t h e e x p e r i m e n t a l l y observed i n f r a
red properties.
EX PER I MENTAL
D e t a i l s o f t h e sample p r e p a r a t i o n and i n f r a r e d s t u d i e s a r e as
described previously (4). 100% exchange o f Na by NH4 (NH4Y-100) was
achieved by t r e a t i n g t h e sample w i t h c o n c e n t r a t e d NH&l under r e f l u x
c o n d i t i o n s f o r s e v e r a l weeks. Subsequent c a l c i n a t i o n g i v e s r i s e t o
HY-100. For benzene, t o l u e n e and o-xylene s a t u r a t i o n o f t h e a d s o r p t i o n
s i t e s was achieved r a p i d l y , however f o r p-xylene, m-xylene and cumene t h e
o r g a n i c vapour had t o be l e f t i n c o n t a c t w i t h t h e z e o l i t e d i s c f o r 1 hour
f o r reasonable coverages t o be a t t a i n e d .
690
:I
::
z
s
p
v1
B
bp
\J
3600 3400 3200 3600 3400 3200
~/c,'~ p/c In-i
F i g 1 . E f f e c t o f a d s o r D t i o n on F i g . 2. E f f e c t of a d s o r p t i o n on
t h e hydroxyl s t r e t c h i n g ' region of t h e hydroxyl s t r e t c h i n g x g i o n o f
HY-100. ( a ) HY-100, ( b ) HY-1001 HY-100. ( a ) HY-100, ( b ) rlY-lOO/
benzene, ( c ) HY-lOO/toluene, p-xylene, ( c ) HY-lOO/m-xylene,
( d ) HY-lOO/o-xylene. ( d ) HY-lOO/cumene.
691
TABLE 1
Observed and t h e o r e t i c a l p e r t u r b a t i o n s o f h . f . z e o l i t e hydroxyi band
2
Adsorb a t e t
'obs.
Ap2 6
- -
42 M't
E
-
P
( ", ''talc.
pl Elql P1 41 E
Benzene 2.274 310 5.33 3.729 1.093 2.31 1.61 5.33 2.37 1.49 5.61 300
To1 uene 2.379 350 6.88 4.070 1 .lo6 2.57 1.58 6.64 2.54 1.51 6.45 330
0- Xy 1e ne 2.568 380 8.82 4.330 1.128 2.95 1.47 8.73 2.91 1.55 8.47 410
m-Xy 1e ne 2.374 350 - - - - - - 2.53 1.51 - 330
p-Xylene 2.270 300 - - - - - - 2.35 1.48 - 295
Cumene 2.380 340 - - - - - - 2.54 1.51 - 330
693
qE as
qE P = [I - $(v/uo) - v / u o ~ + l / 1 6 ( u / v o ~ ) D
(1)
P
where
a = wD
)
i
I f t h e wave number o f t h e f r e e OH v i b r a t i o n i s 3750 cm-’ and t h e
d i s s o c i a t i o n energy ( D ) o f t h e OH bond i s 461.077 kJmol-’, then t h e
p o l a r i s a t i o n f o r c e (qE ) can be deduced f r o m t h e r a t i o v/uo. Equation 1
P
a l s o enables us t o c a l c u l a t e t h e v a r i a t i o n i n t h e p o l a r i s a t i o n f o r c e (Eq)
on t h e hydrogen atom o f t h e OH o s c i l l a t o r b r o u g h t about by t h e p h y s i c a l
a d s o r p t i o n of gases and vapours and i t can be expressed as
molecules h a v i n g d i e l e c t r i c c o n s t a n t 12 i n t h e v i c i n i t y o f t h e OH d i p o l e .
B e f o r e a d s o r p t i o n , t h i s d i p o l e i s surrounded by a vacuum w i t h t = 1.0 and
M*/M and Eh/E a l s o equal t o 1.0.
The i n c r e a s e d i n t e n s i t y o f t h e p e r t u r b e d band can a l s o be s i m u l a t e d .
The r a t i o o f t h e absorbance o f t h e p e r t u r b e d ( A ) and u n p e r t u r b e d (Au) OH
P
bands can be shown ( 3 , 5 ) t o be
A /A = v / v (q /qUl2r
P U O P
where
2
( ‘ = [C(v/v,) - 31 ( C - 2 )
-
c [v/vo) - 2 I L (C - 3)
Table 1 g i v e s t h e observed f r e q u e n c y s h i f t s a f t e r a d s o r p t i o n o f
benzene, t o l u e n e , o-xylene, m-xylene, p-xylene and cumene. As was
695
REFERENCES
SUMMARY
The i n f l u e n c e o f t h e a c i d i t y o f z e o l i t e s on t h e f o r m a t i o n o f u n s a t u r a t e d
carbenium i o n s from propene and a l l e n e was i n v e s t i g a t e d by combined U V - V I S - I R
spectroscopy. The h i g h e r t h e B/L a c i d i t y r a t i o t h e l o w e r t h e frequency o f t h e
a l k e n y l carbenium i o n s and t h e l e s s i n t e n s e t h e g e n e r a t i o n o f monoenyl i o n s
from b o t h a l l e n e and propene o v e r z e o l i t e s HNaY-FAU and HNa-ZSM-5.
INTRODUCTION
The a d s o r p t i o n o f o l e f i n s on z e o l i t e s r e s u l t s i n t h e f o r m a t i o n o f various
s u r f a c e species. G e n e r a l l y t h e s t r e n g t h o f t h e i n t e r a c t i o n between t h e a c t i v e
s i t e s and t h e o l e f i n molecules can be c h a r a c t e r i z e d by t h e frequency s h i f t of
t h e C=C double bond fundamental.
On e s s e n t i a l l y n o n a c i d i c z e o l i t e s , e.g. z e o l i t e A exchanged w i t h a l k a l i n e ,
a l k a l i n e e a r t h o r t r a n s i t i o n metal i o n s , t h e s h i f t o f t h e C=C s t r e t c h proved
t o be p r o p o r t i o n a l t o t h e " p o l a r i z i n g power", i . e . the charge/radius r a t i o o f
t h e c a t i o n s f o r butenes ( r e f . l ) , propene ( r e f . 2) and a l l e n e ( r e f . 3 ) .
On acidic z e o l i t e s the adsorption o f o l e f i n s leads t o t h e generation of
s a t u r a t e d as w e l l as u n s a t u r a t e d carbenium i o n s , b e i n g proven w i t h different
e x p e r i m e n t a l techniques ( r e f . 4 ) .
A c i d i c z e o l i t e s g e n e r a l l y c o n t a i n Bronsted and Lewis a c i d s i t e s , which b o t h
a r e i n v o l v e d i n t h e f o r m a t i o n o f c a r b o c a t i o n s f r o m hydrocarbons. B r o n s t e d a c i d
c e n t e r s may be r e s p o n s i b l e f o r t h e g e n e r a t i o n o f carbonium i o n s f r o m p a r a f f i n s
(ref. 5), a l k y l carbenium i o n s f r o m o l e f i n s ( r e f . 6 ) and a l k e n y l carbenium
ions from d i e n s ( r e f . 7), w h i l e on Lewis a c i d s i t e s t h e f o r m a t i o n o f alkyl
carbenium i o n s from p a r a f f i n s ( r e f . 8 ) and a l k e n y l i o n s f r o m o l e f i n s ( r e f . 9 )
may o c c u r .
Although t h i s generalization o f the formation o f carbocations i n zeolites
is w i d e l y accepted, some i m p o r t a n t d e t a i l s c o n c e r n i n g t h e i n f l u e n c e of the
r a t i o o f t h e Bronsted t o Lewis a c i d i t y (B/L) and/or t h e c o n c e n t r a t i o n o f acid
698
EXPERIMENTAL
HNaY-FAU and HNaZSM-5 z e o l i t e s were used i n t h e e x p e r i m e n t s . Their parent
m a t e r i a l s , NH4NaY-FAU and NHqNaZSM-5, were p r e p a r e d by i o n exchange f r o m t h e i r
sodium forms, c h a r a c t e r i z e d by XRD, K B r - m a t r i x I R and TG, and f o u n d t o be
well-crystalline. The u n i t c e l l c o m p o s i t i o n s determined by AAS a r e l i s t e d in
Table 1.
F o r t h e s p e c t r o s c o p i c measurements s e l f - s u p p o r t i n g w a f e r s were p r e s s e d f r o m
the ammonium forms of t h e samples, deammonated and outgassed at three
different temperatures (673, 773, 873 K ) i n t h e respective optical cell
equipped w i t h e i t h e r q u a r t z o r NaCl windows i n o r d e r t o obtain samples of
d i f f e r e n t amounts o f B r o n s t e d and Lewis a c i d s i t e s . The a c i d i t y o f t h e samples
was determined by I R spectroscopy u s i n g p y r i d i n e as probe molecule (for
d e t a i l s see r e f . l o ) , and l i s t e d i n Table 1.
The I R s p e c t r a were r e c o r d e d on a P e r k i n - E l m e r 225 s p e c t r o m e t e r , w h i l e the
UV-VIS experiments were performed on a Cary 17 s p e c t r o m e t e r operating under
computer c o n t r o l .
Quantum chemical c a l c u l a t i o n s were c a r r i e d o u t u s i n g the PcMol program
system developed f o r microcomputers ( r e f . 11). The MNDO-HE (ref. 12) and
CNDO/S (ref. 13) methods were a p p l i e d f o r t h e c a l c u l a t i o n of the lowest
v e r t i c a l s i n g l e t e x c i t a t i o n e n e r g i e s (LVSEE). The g e o m e t r i e s o f carbocations
were o p t i m i z e d w i t h i n t h e MNDO a p p r o x i m a t i o n . For calculation o f the UV-VIS
s p e c t r a i n t h e case o f a l l y 1 c a t i o n 30 and i n t h e case o f a l l o t h e r carbenium
ions 90 monoexcited c o n f i g u r a t i o n s were taken i n t o account in the con-
figuration interaction.
RESULTS
Fig. 1 shows t h e U V - V I S s p e c t r a o f propene adsorbed on sample No. 6. A f t e r
i n t r o d u c t i o n o f 1.33 kPa propene i n t o t h e c e l l a band was observed a t 318 nm.
At room temperature t h e p o s i t i o n o f t h i s band was s h i f t e d to higher wave-
l e n g t h s w i t h i n c r e a s i n g c o n t a c t t i m e . Heat t r e a t m e n t a t 323 K f o r 1 h r e s u l t e d
in the development o f a new band a t 370 nm and simultaneously the high-
frequency (HF) band s h i f t e d t o 323 nm (see spectrum 4 ) . Upon evacuation at
298, 373 and 473 K t h e i n t e n s i t i e s o f t h e HF bands decreased and their
699
Concentrations o f
Sample Zeolite U n i t c e l l compositions acid s i t e s i n B/L
mol /kg
No. Bronsted Lewis
1 HNaY/673 (NH4)42 Na16 0.441 0.082 5.4
2 HNaY/773 (NH4)42 Na16 0.058 0.305 0.2
3 HNaY/873 (NH4)42 Na16 0.007 0.156 0.04
4 HNaZSM-5/673 (NH4)1.2 Na0.06 ZSM-5 0.033 0.008 4.0
5 HNaZSM-5/773 ( N H 4 ) i a 2 Na0.06 ZSM-5 0.028 0.013 2.2
6 HNaZSM-5/873 (NH4)1.2 Na0.06 ZSM-5 0.018 0.015 1.2
F i g . 3. U V - V I S s p e c t r a o f F i g . 4. U V - V I S s p e c t r a o f
propene adsorbed on samples a l l e n e adsorbed on samples
1-6 (subsequent t o adsorp- 1 - 6 (subsequent t o adsorp-
t i o n (a), a f t e r 1 h ( b ) ) . t i o n (a), a f t e r 1 h ( b ) ) .
701
z e o l i t e was o n l y p a r t l y r e s t o r e d i n t h e OH s t r e t c h i n g range.
A l l e n e t r a n s f o r m s e a s i l y t o propyne o v e r z e o l i t e c a t a l y s t s ( r e f . 15). This
c o n v e r s i o n c o u l d be d e t e c t e d a l s o on a c i d i c z e o l i t e s by t h e appearence o f the
bands due t o t h e CIC and C-H s t r e t c h i n g v i b r a t i o n s o f adsorbed propyne a t 2116
and 3275 cm-I, r e s p e c t i v e l y . P a r a l l e l t o t h i s i s o m e r i z a t i o n a f a s t o l i g o m e r i z a -
t i o n v i a a l k e n y l carbenium i o n s takes place, i n d i c a t e d by t h e development of
the band c h a r a c t e r i s t i c f o r these t y p e s o f i o n s a t 1505 cm’ and the typical
o l i g o m e r bands a t 1480 and 1380 c d . I t i s w o r t h w i l e t o m e n t i o n t h a t t h e band
o f t h e a l k e n y l carbenium i o n s a t 1505 c f l ’ c o u l d be d e t e c t e d more e a s i l y on t h e
zeolites of l e s s Bronsted a c i d i t y . Upon h e a t t r e a t m e n t t h e colour of the
sample changed f r o m w h i t e t o y e l l o w and a t 473 K t o brown. I n t h i s case the
o r i g i n a l spectrum i n t h e OH r e g i o n c o u l d n o t be r e s t o r e d .
DISCUSSION
The bands observed i n t h e ranges 280-330, 360-380 and 430-470 nm are
a t t r i b u t e d t o t h e n-T: t r a n s i t i o n s o f mono-, d i - and t r i e n y l i c carbenium i o n s .
It has a l r e a d y been s t a t e d t h a t these wavelengths c h a r a c t e r i s t i c f o r alkenyl
carbenium ions formed i n z e o l i t e s agree w e l l w i t h those calculated by the
Sorensen e q u a t i o n d e s c r i b i n g t h e frequency dependence o f p o l y e n y l i c carbenium
i o n s as a f u n c t i o n o f t h e number o f c o n j u g a t e d double bonds i n t h e respective
ion (ref. 4c). Furthermore, the c a p a b i l i t y f o r a1 k e n y l i o n formation of
different hydrocarbons and t h e i r d e r i v a t i v e s f o l l o w s t h e same sequence as
observed i n s u p e r a c i d s o l u t i o n s ( r e f . 7 ) .
As far as t h e i n f l u e n c e o f t h e a c i d i t y o f z e o l i t e s i s concerned i t was
found e a r l i e r t h a t t h e f o r m a t i o n o f mono-, d i - and t r i e n y l i c carbenium ions
slows down w i t h decreasing o v e r a l l a c i d i t y ( r e f s . 4c,17). The results of
quantum chemical c a l c u l a t i o n s u s i n g t h e MNDO e f f e c t i v e charge model rendered
good qualitative c o r r e l a t i o n t o the spectroscopic observations, i .e. the
higher t h e r e l a t i v e p e r m i t t i v i t y o f t h e s o l v e n t (comparable w i t h t h e acidity
of z e o l i t e s i n a coarse f i r s t a p p r o x i m a t i o n ) t h e more s t a b l e i s the alkenyl
carbenium i o n ( r e f . 1 6 ) .
The common f e a t u r e o f t h e s p e c t r a o f adsorbed propene and a l l e n e (see F i g s .
1-2) i s t h e s h i f t o f t h e U V - V I S band t o h i g h e r wavelengths w i t h c o n t a c t time
and i t s r e v e r s i o n upon e v a c u a t i o n . T h i s can be e x p l a i n e d by: t h e band p o s i t i o n
of monoenylic carbenium i o n s (observed g e n e r a l l y i n t h e 275-320 nm range in
s u p e r a c i d s o l u t i o n ) b e i n g s e n s i t i v e t o t h e s u b s t i t u e n t groups (refs. 18-20).
While the i n s e r t i o n o f an a d d i t i o n a l double bond g i v e s r i s e t o a frequency
jump by about 60 nm, the e x t e n s i o n o f t h e carbon chain or formation of
branched o l i g o m e r s r e s u l t s o n l y i n a smooth downscale f r e q u e n c y shift, being
accomplished by c o n s e c u t i v e r e a c t i o n s , as b o t h propene and a l l e n e o l i g o m e r i z e
702
y 3 t y3+
CH3-CH-CH-CH-CH2 CH3-C-CH-CH-CH3 CH2- C- CH- CH2- CH3
-_____ -_-- __---
t h e r e should be an e q u i l i b r i u m m i x t u r e o f v a r i o u s monoenyl carbenium i o n s the
commonness o f which c o n s i s t s i n a c 6 backbone a b s o r b i n g a t d i f f e r e n t frequen-
c i e s . The s p e c t r o s c o p i c measurements were performed on z e o l i t e s w i t h d i f f e r e n t
B/L r a t i o s . I t i s accepted t h a t t h e B r o n s t e d a c i d s i t e s p l a y t h e dominant r o l e
i n oligomerization o f olefins, b u t t h e p a r t i c i p a t i o n o f Lewis c e n t e r s i n t h i s
reaction cannot be n e g l e c t e d ( r e f s . 21,22). It f o l l o w s t h a t the higher the
amount of Bronsted a c i d s i t e s , t h e more pronounced t h e oligomerization of
olefins and consequently the a l k e n y l carbenium ions formed during this
reaction absorb a t h i g h e r wavelengths. This i s the experimental observation
w i t h b o t h propene and a l l e n e on b o t h t y p e s o f z e o l i t e s (see F i g s . 3 , 4 ) .
In the s p e c t r a o f adsorbed a l l e n e t h e p r e v a i l i n g band was found in the
range 359-380 nm characteristic f o r dienyl carbenium ions. Assuming the
f o l 1 owing t r a n s f o r m a t i on : t
CH2-C-CH-CH-CH2
-_------
t h e g e n e r a t i o n o f i n c r e a s i n g l y u n s a t u r a t e d carbenium i o n s s h o u l d be expected.
The i d e a was t h a t i f t h e number o f B r o n s t e d a c i d s i t e s o f t h e z e o l i t e sample
was decraesed by d e h y d r o x y l a t i o n , i n s t e a d o f l o w e r i n g t h e degree o f ammonium
ion exchange (ref. 4c), the e x i s t e n c e o f more and more simple monoenyl
carbenium ions s h o u l d be observed by U V - V I S spectroscopy, since with in-
creasing dehydroxylation the strength o f Bronsted acid s i t e s probably also
increases, t h e r e b y p r o m o t i n g t h e s t a b i l i t y o f a g i v e n carbenium i o n . As shown
in Fig, 4 our e x p e c t a t i o n came t r u e : t h e lower the B/L ratio the more
703
CONCLUSIONS
The lower the B/L a c i d i t y r a t i o o f t h e z e o l i t e , the higher w i l l be the
frequency o f t h e a l k e n y l carbenium i o n s formed f r o m propene and a l l e n e on b o t h
types of zeolites. T h i s c h a r a c t e r i s t i c can be a t t r i b u t e d to the enhanced
f o r m a t i o n o f o l i g o m e r s on t h e z e o l i t e s o f h i g h e r B r o n s t e d a c i d i t y .
The h i g h e r t h e B/L r a t i o o f t h e sample, the l e s s intenses the formation o f
monoenyl carbenium i o n s a b s o r b i n g a t 280-310 nm. T h i s f a c t m i g h t be e x p l a i n e d
by assuming an increase o f the strength o f the Bronsted acid sites with
decreasing c o n c e n t r a t i o n s (as a r e s u l t o f dehydroxyl a t i o n ) , thereby promoting
t h e s t a b i l i t y o f t h e monoenyl carbenium i o n s formed f r o m a l l e n e .
ACKNOWLEDGEMENT
One o f t h e a u t h o r s ( I . K.) thanks t h e Alexander von Humboldt F o u n d a t i o n f o r
a r e s e a r c h f e l l o w s h i p . The f i n a n c i a l s u p p o r t o f t h e Hungarian Academy o f
Sciences (No. OTKA 217/88) and t h e Deutsche Forschungsgemeinschaft i s g r a t e -
f u l l y acknowledged
REFERENCES
1 H F o r s t e r , R . Seelemann, J. C . S . Faraday Trans. I , 74 (1978) 1435
2 H F o r s t e r , J. Seebode, Z e o l i t e s , 3 (1983) 63
I . K i r i c s i , G. T a s i , P . F e j e s , F. Berger, J . Mol. C a t a l . , 51 1989) 341
3 I . K i r i c s i , G. T a s i , I. Hannus, P . F e j e s , H. F o r s t e r , J. Mol. C a t a l . ,
i n press
4 ( a ) M. Zardkoohi, J. F . Haw, J. H. Lunsford, J. Am. Chem. SOC , 109
(1987) 5278
( b ) A . S. Medin, V . Yu. Borovkov, V . B. K a z a n s k i i , K i n e t i k a i K a t a l iz.
30 (1989) 177
( c ) H . F o r s t e r , 3 . Seebode, P . F e j e s , I . K i r i c s i , J . C . S. Faraday Trans.
I , 83 (1987) 1109
5 E. A . Lombardo, R . P i e r a n t o z z i , W. K. H a l l , J . C a t a l ., 110 (1988) 171
6 J . P . van den Berg, J. P . Wolthuizen, A. D. H. Clauqe, G. R . Hays,
R . Huis, J . H. C . van H o o f f , J. C a t a l . 80 (1983) 130
7 P. Fejes, H. F o r s t e r , I . K i r i c s i , J. Seebode, i n " S t r u c t u r e and R e a c t i v i t y
of M o d i f i e d Z e o l i t e s " , D. A. Jacobs,N. I . Jaeger, P. J i r u , V . B . K a z a n s k i i
G. S c h u l z - E k l o f f ( e d s . ) , E l s e v i e r , Amsterdam, 1984, p. 9 1
8 M. L . Poutzma, i n " Z e o l i t e Chemistry and C a t a l y s i s " , Am. Chem. SOC.
Washington, Ed. J . A . Rabo (ACS Monograph 171) pp. 437
9 H. F o r s t e r , S. Franke,J. Seebode, J. C . S. Faraday Trans. I , 79 (1983) 373
10 I . K i r i c s i , G. T a s i , H. F o r s t e r , P . F e j e s , A c t a Phys. e t Chem. Szeged,
33 (1987) 69
11 G. Tasi, I . K i r i c s i , P . F e j e s , H. F o r s t e r , S. Lovas, Magy. Kem.
F o l y o i r a t , 95 (1989) 520
705
AUTHOR INDEX
Preobrazhensky. A.V
Prilipko. A.1
.......357
.............563
Pritzkow, W............... 549
Rao. B.S..................347
Raurell. G.L.............. 387
Rees. L.V.C................61
Reschetilowski. W.........529
Richter, M................631
Richter-Mendau. J.........501. 549
............501
Rozwadowski, M
.............. 233
Ruthven. D.M
.................663
Salzer. R
...............75
Schollner. R
..............457
Schoonman, J
Schreier. E................. 1. 631
Schroder. K.-P............ 435
Schulz. I.................415
Schulz-Ekloff. G..........327
Schwartz. S............... 491
Schwieger. W.............. 185
Senchenya. 1.N............653
............347
Shiralkar. V . P
Shpiro, E.S............... 357
Siegel. H................. 367
Sonntag. E................ 537
Spoto, G.................. 671
Springuel-Huet, M.A.......219
Steinberg, K.-H...........367. 663
Suboti6. B................ 573
Svensson. A............... 327
Sychev. M.................581
Szulzewsky. K............. 549. 631
Tagiyev. D.B.............. 623
Tasi, G...................697
Tatsumi. T................203
Telbiz. G.M...............563
Timm, D...................415
Tkachenko. 0.P............357
Tominaga. H............... 203
Tuleuova. G.J.............357
Ullmann. G................367
Van Bekkum, H............. 457,467
Vasina. T.V...............357
Vaughan, D.E.W............275
Von Ballmoos. R........... 171
Voogd. P.................. 467
Vorbeck. G................ 631
Vtjurina. L.M.............287
Wehner. K ................. 415
Weitkamp. J ................21.297. 645
Wichterlova. B ............387
Wieker. W .................315
xu. z..................... 233
Zecchina. A ...............671
Zhdanov. S.P .............. 287
Zholobenko. V.L ...........425
Zibrowius, B
Zmierczak. W
................1,537,549, 631
..............377
This Page Intentionally Left Blank
711
SUBJECT INDEX
Acetone adsorption ...............
Acetone. conversion from
337
.........405
Acid-base pair
Acidity
...................1171.89.563.631.681. 697
............................
Acid site characterization
Activation
.......133
....................... 663
Active sites ..................... 425
Adsorption .......................
Adsorption of CO .................133.157.435.479.
671
689
Allene...........................
Alloying particles ...............357
697
Diffusion
Diffusivity
........................
...................... 257
2331305145714671479
Dispersion .......................
Electronegativity ................
327
157
Electronic structure .............653
Erionite ......................... 663
Ethane hydrogenolysis ............ 357
Ethylbenzene conversion ..........6 3 1
EXAFS ............................ 357
Extraction of aluminium..........415
Extrudates....................... 491
Faujasite........................ 27Sl 327
FCC catalysts.................... 171
Ferrisilicates...................6 3 1
Fe-ZSM-5......................... 631
Framework density distribution...247
Heteroatom incorporation.........5 8 1
Heterogeneous nucleation.........603
n-Hexane cracking................425
High pressure chromatography.....479
H-mordenite...................... 347
Host/guest chemistry ..............2 1
Hybrid catalyst..................203
Hydrocarbon pyrolysis ............315
Hydrothermal crystallization.....623
Hydroxyls......................... ag1563168i
H-ZSM-5 zeolite.................. 3 3 7 14 2 5
H-ZSM-12 ....................... ..347
Influence of geometry ............653
In-situ study .................... 663
Interface........................ 257
Intergrowth of structure.........219
IR diffuse reflectance spectr ....1 1 7
IR spectroscopy ..................4 2 5 1 5 3 7 1 6 6 3 1 6 8 1
Isomerization .................... 3 0 5
Isomorphous substituted ZSM-5 ....5 8 1
Isomorphous substitution .........537
Iso-paraffins .................... 203
Isopropylation of benzene ........347
Isotherms ......................... 4 4
Kinetics ......................... 2a 7 1 3 0 5
Kinetics of cumene sorption ......347
KVS-5 molecular sieve ............5 8 1
La-H-Y ...........................
Large crystals ...................35 40 7l I 5 a i
Large pore zeolites
Lewis acidity
..............347
.................... i1 7 1 6 5 3
Linde L .......................... 275
Liquid phase adsorption ........... 7 5
MAS NMR .......................... 397
MAS N M R ( 2 7 Al) .................. 529
Matrix activity..................1 7 1
Matrix vs zeolite................1 7 1
Mechanism .......................... il i a 5
Membranes ........................ 2 5 7 1457
Methane aromatization............357
Methane splitting................367
Methanol ......................... 563
Methanol conversion ..............3 1Sl653
Methanol conversion to olefins...4 1 5
713
Methanol-to-olefins ................1
Methylation ...................... 305
Microdynamics .................... 445
Modelling ........................ 257,689
Modelling by computer ............ 435
Modification ....................... 1. 1171327
Molecular sieve ..................501
Mountainite ...................... 623
MO-Y ............................. 377
Multinuclear N M R .................591
Nay ............................... 4 7 1 61
Ni-Mo-Y .......................... 377
Nitrogen bases ...................297
Ni-ZSM-5 catalyst................367
N M R in alumino-galloferrierite...613
NMR spectroscopy ............337
(13c)
NMR spectroscopy. multinuclear
Normal coordinate analysis
...
537. 549
.......
511
Nucleation .......................
287. 591
Nucleation kinetics ..............
573
Oligomerization ..................
491
Organic intermediates ............
297
Para selectivity
Path of oxidation
.................
387
................
405
Pelletization .....................
75
Pentasil-type ....................
185
Pentasil zeolites .................
75
Permeation .......................
457
Phase transitions in AlPOs .......
549
Piperazine .......................
297
Porosity .........................
247
Propene ..........................
Properties
697
.......................
623
Proton-MAS-NMR
Pt-Cr pentasils
....................
89
..................
357
Pulsed field gradient N M R .........
89. 445
Quasi-elastic neutron scattering.445
Realumination ....................
529
Regeneration .....................
Restoration of active sites
315
......
405
Restoration of void volumes ......
405
SAPO-5 ........................... 5011537
SAPO-37 .......................... 591
SAPO-40 ........................ ..591
Secondary synthesis..............529
Self-diffusion .................... a gI445
Separation........................ 61
Shape selective catalysis .........21
Shape selective photochemistry ....21
Shape-selectivity ................387
Ship-in-the-bottle catalysts......21
Silicalite .......................233.457. 4 6 7 1 6 7 1
Silicalite-1 ......................
61.435
Silicon incorporation ............
537
Single crystal ...................
457
Sorption ..........................611257
Spectroscopy .....................
Strength of acid sites
697
...........
133
Structure defect .................219
Structure effect .................
157
714
Xenon-=
XRD
........................ 219
.............................. 549
XRD in alumino-galloferrierite
para-Xylene
...613
...................... 435
meta-Xylene isomerization
Zeolite 13 x
........631
..................... 479
Zeolite A ........................ 233
Zeolite activity
Zeolite 8
................. 603
........................ 171
Zeolite genesis
Zeolite H-ZSM-5
..................
.................. 275
Zeolite-like silicates ...........397623
Zeolite NaX
Zeolites
...................... 511
......................... 20714451689
Zeolite sub-units
Zeolite synthesis
................
................275 645
Zeolite X
Zeolite Y
........................
........................ 233
563
Zeolite ZSM-57
ZSM-~
...................
............................ 645
3 0 ~ 1 3 ~ ~ 1 3 a 7 1 4 3 5 1 ~ ~ ~ l ~ ~ ~ 1
ZSM-12 ........................... 603
ZSM-35 ........................... 645
ZSM-57 ........................... 645
715