Perspectives in Molecular Sieve Science - American Chemical Society

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Ν. Y. Chen Central Research Laboratory, Mobil Research and Development Corporation, Princeton, NJ 08540

Summary Shape selective catalysis with molecular sieve zeolites has progressed in its first thirty years to become an established branch of catalytic science. Since the first demonstration of selective n-paraffin conversion over 5A molecular sieves, increased insight into how these catalysts function has created opportunities for the development of a number of new industrial processes. In the meantime, new characterization tools such as NMR, STEM, EXAFS, FTIR, and synchrotron XRD, etc., have allowed us to peer into the very heart of the zeolite and discern the nature and orientation of the active tetrahedral sites as well as determine the dimensions and connectivity of the zeolite pore systems. Today we find shape selective catalysis 30 years old but far from mature. Synthesis and preparation of molecular sieves has expanded to over 200 combinations of chemical compositions and crystal structures. Indeed, the number of elements which can be inserted into the crystal framework either by isomorphous substitution or by direct synthesis has grown dramatically in recent years. This paper presents a personal overview of the past progress and future horizons of shape selective catalysis from a practitioner's viewpoint. After 30 years of effort, we can now safely say that shape selective catalysis has established itself as a new and continually evolving branch of heterogeneous catalysis. I would like to give you a personal view of the major advances made with respect to the general principles of catalyst design and the industrial applications of shape selective catalysis. 0097-6156/88/0368-0468$06.00/0 © 1988 American Chemical Society

Flank and Whyte; Perspectives in Molecular Sieve Science ACS Symposium Series; American Chemical Society: Washington, DC, 1988.

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Molecular

Shape-Selective Catalysis at the SO- Year Mark sieve

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zeolites

As we a l l know, t h e r e a r e two a s p e c t s t h a t make z e o l i t e s unique. F i r s t of a l l , being c r y s t a l s , t h e i r i n t r a c r y s t a l l i n e s u r f a c e i s an i n h e r e n t p a r t o f t h e c r y s t a l s t r u c t u r e and hence t h e y a r e t o p o l o g i c a l l y w e l l defined. T h i s i s i n sharp d i s t i n c t i o n t o the i l l d e f i n e d amorphous s o l i d s we a r e f a m i l i a r w i t h . The a v a i l a b i l i t y o f s o l i d s w i t h s u c h a l a r g e and w e l l d e f i n e d s u r f a c e a r e a i s c e r t a i n l y e x c i t i n g and w e l c o m i n g news t o u s . Secondly, the diameter of t h e i r pores i s of s i m i l a r m a g n i t u d e t o t h a t o f many o r g a n i c m o l e c u l e s o f interest. M o l e c u l a r s i e v i n g and shape s e l e c t i v i t y , p r e v i o u s l y unknown, became p o s s i b l e w i t h man-made catalysts. T h e r e f o r e , w i t h z e o l i t e s we c a n b e g i n t o d i s c u s s t h e c o n c e p t o f d e s i g n i n g n o v e l c a t a l y s t s on a m o l e c u l a r l e v e l - i t i s a f a s h i o n a b l e t h i n g these days t o t a l k about molecular engineering or nanotechnology. Of c o u r s e , we a r e f a r f r o m b e i n g s a t i s f i e d w i t h t h e c u r r e n t s t a t u s of c a t a l y s t design. To b e g i n w i t h , we have y e t t o s y n t h e s i z e a new s t r u c t u r e e n t i r e l y by t h e p r i n c i p l e s o f m o l e c u l a r engineering. I n f a c t , a l l o f t h e new s t r u c t u r e s were d i s c o v e r e d by c h a n c e and by e x p e r i e n c e r a t h e r t h a n by design. N e v e r t h e l e s s , many a d v a n c e s have b e e n made. F o r example, t h e s y n t h e s i s and p r e p a r a t i o n o f new m a t e r i a l s has expanded t o o v e r 200 c o m b i n a t i o n s o f c h e m i c a l c o m p o s i t i o n s and c r y s t a l s t r u c t u r e s , n o t t o mention the p o s s i b l e v a r i e t y of m o l e c u l a r l y engineered l a y e r e d s t r u c t u r e s s u c h as t h e MELS f r o m C a t a l y t i c a (JL) and many o t h e r p i l l a r e d c l a y s . W h i l e c l a s s i c a l z e o l i t e s c o n t a i n S i and A l , t h e s u b s t i t u t i o n o f a d d i t i o n a l e l e m e n t s s u c h as Ga, Ge, B, P, e t c . , i n framework p o s i t i o n s has b e e n a c h i e v e d . I n d e e d , t h e number o f e l e m e n t s w h i c h c a n be i n s e r t e d i n t o t h e c r y s t a l framework e i t h e r by i s o m o r p h o u s s u b s t i t u t i o n o r by d i r e c t s y n t h e s i s has grown d r a m a t i c a l l y i n recent years (2). The s y n t h e s i s o f aluminum p h o s p h a t e - b a s e d m a t e r i a l s has a l s o l e d t o some new f r a m e w o r k s and new c o m p o s i t i o n s o f known frameworks. E x t e n s i v e work on t h e s e new m a t e r i a l s has j u s t begun ( 3 - 4 ) . Z e o l i t e s derive t h e i r a c i d i t y or c a t a l y t i c a c t i v i t y f r o m t h e p r o t o n a s s o c i a t e d w i t h t h e framework aluminum. R e p l a c e m e n t o f aluminum by t h e o t h e r t h r e e v a l e n t elements c o u l d a l s o l e a d t o the g e n e r a t i o n of Bronsted a c i d s i t e s . However, one n e e d s t o e x e r c i s e caution i n proclaiming unusual c a t a l y t i c p r o p e r t i e s b e f o r e one t h o r o u g h l y u n d e r s t a n d s t h e n a t u r e o f t h e s e materials. F o r example, many s t u d i e s have b e e n r e p o r t e d on t h e n a t u r e o f t h e a c i d i t y o f b o r o n ZSM-5 (5-6-7-8). A l t h o u g h p h y s i c a l measurements (8-9) i n d i c a t e t h a t the p r o t o n i c s i t e a s s o c i a t e d w i t h the


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framework b o r o n e x h i b i t s some weak a c i d i c p r o p e r t i e s , t h e s t u d i e s o f Chu and Chang (8) showed t h a t t h e c a t a l y t i c a c t i v i t y o f B o r o n ZSM-5 was due t o t h e aluminum c o n t a m i n a n t i n t h e s a m p l e . As f a r a s shape s e l e c t i v e c a t a l y s i s i s c o n c e r n e d , the s t r u c t u r e c h a r a c t e r i s t i c o f g r e a t e s t i n t e r e s t i s the pore/channel system o f these m o l e c u l a r s i e v e s . As we know, d e p e n d i n g o n t h e l a r g e s t c h a n n e l , z e o l i t e s a r e c h a r a c t e r i z e d a s s m a l l , medium o r l a r g e p o r e i f t h e y c o n t a i n a p e r t u r e s made by r i n g s o f 8, 10 o r 12 l i n k e d tetrahedra. I n a d d i t i o n t o t h e d i f f e r e n c e i n s i z e and s h a p e , t h e c h a n n e l s y s t e m i n t h e s e z e o l i t e s may be o n e d i m e n s i o n a l a s i n ZSM-48 (10) o r m u l t i d i m e n s i o n a l as i n ZSM-5. T h e s e c h a n n e l s c o u l d be r e l a t i v e l y u n i f o r m i n s i z e o r they c o n s i s t of i n t e r c o n n e c t i n g supercages. Principles

of catalyst

design

The d e s i g n o f shape s e l e c t i v e c a t a l y s t s may be d e s c r i b e d as the s c i e n c e o f c o u p l i n g chemical r e a c t i o n s w i t h s o r p t i o n and d i f f u s i o n c h a r a c t e r i s t i c s o f t h e z e o l i t e t o a l t e r t h e r e a c t i o n pathway and t h e p r o d u c t s e l e c t i v i t y o f known c h e m i c a l r e a c t i o n s . R e a c t i o n s e l e c t i v i t y b a s e d on t h e p r i n c i p l e o f m o l e c u l a r e x c l u s i o n o r m o l e c u l a r s i e v i n g a c t i o n was d e m o n s t r a t e d many y e a r s a g o . S t e r i c i n h i b i t i o n of the formation of bulky r e a c t i o n intermediates can a l s o l e a d t o unexpected selectivity. T h i s i s known a s s p a t i o s e l e c t i v i t y o r transition state selectivity. C s i c s e r y f i r s t proposed t h i s i n 1978 i n h i s s t u d y w i t h m o r d e n i t e ( 1 1 ) . With medium p o r e z e o l i t e s , t h e r e l a t i v e l y s l o w r a t e o f c r a c k i n g o f 3 - m e t h y l p e n t a n e compared t o t h a t o f n— h e x a n e , known a s t h e C o n s t r a i n t I n d e x o f t h e s e z e o l i t e s (12) i s a t y p i c a l example o f t h i s t y p e o f shape selectivity. The r e a c t i o n i n t e r m e d i a t e f o r 3-methylpentane i s s t e r i c a l l y c o n s t r a i n e d i n the pores o f ZSM-5. I n a d d i t i o n t o s i z e e x c l u s i o n and s t e r i c i n h i b i t i o n , t h e i n t e r m o l e c u l a r f o r c e s between t h e z e o l i t e and s o r b a t e m o l e c u l e s o f f e r o p p o r t u n i t i e s t o a c h i e v e u n i q u e s e l e c t i v i t y b a s e d on c o m p e t i t i v e sorption properties of various z e o l i t e s . Variables such as s i l i c a t o alumina r a t i o , the nature o f the cation s p e c i e s and t h e g e o m e t r y o f t h e c h a n n e l s have b e e n shown t o be i m p o r t a n t f a c t o r s f o r c o n s i d e r a t i o n (13-14). They a l s o c a n c o n t r i b u t e t o c a t a l y s t s t a b i l i t y and r e d u c e d c o k i n g p r o p e n s i t y , two i m p o r t a n t c h a r a c t e r i s t i c s of commercially u s e f u l c a t a l y s t s .


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Design

for diffusion

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c o n s t r a i n e d systems

One may w i s h t o t a k e a d v a n t a g e o f t h e d i f f e r e n c e i n t h e d i f f u s i v i t y of the molecules i n the z e o l i t e channels t o achieve high s e l e c t i v i t y . In t h i s case, b e s i d e s the s e l e c t i o n o f a s p e c i f i c z e o l i t e s t r u c t u r e and c h e m i c a l c o m p o s i t i o n , t h e s u c c e s s f u l d e s i g n o f a shape s e l e c t i v e c a t a l y s t o f t e n depends on t h e a b i l i t y t o a l t e r and c o n t r o l t h e m o r p h o l o g y o f t h e c r y s t a l s and t h e means t o a d j u s t the c o n c e n t r a t i o n of a c t i v e s i t e s w i t h i n each crystal. H i g h s e l e c t i v i t y w i l l r e s u l t when t h e r a t e o f t h e r e a c t i o n s i n v o l v i n g the u n d e s i r a b l e b u l k i e r molecules i s i n the s e v e r e l y d i f f u s i o n c o n s t r a i n e d regime. The o b s e r v e d s e l e c t i v i t y depends on t h e r e l a t i v e r a t e o f r e a c t i o n t o t h a t of d i f f u s i o n of these molecules. It i s o b v i o u s t h a t t h e d e g r e e o f s e l e c t i v i t y c a n be a d j u s t e d by v a r y i n g t h e d i f f u s i o n pathway and i t s a c i d s i t e d e n s i t y (15). The a d v a n c e s o f o u r c a p a b i l i t y i n t h i s a r e a were a i d e d by a number o f r e m a r k a b l e new d e v e l o p m e n t s i n a n a l y t i c a l instrumentation. T h e s e new c h a r a c t e r i z a t i o n t o o l s i n c l u d e , among many, NMR, which p r o v i d e s i n f o r m a t i o n on t h e l o c a l e n v i r o n m e n t o f atoms i n t h e s t r u c t u r e ( 1 6 - 1 7 ) , s y n c h r o t r o n XRD, w h i c h p r o v i d e s v e r y h i g h r e s o l u t i o n x - r a y d a t a f r o m powders ( 1 8 - 1 9 ) , t h e a p p l i c a t i o n of R i e t v e l d a n a l y s i s of x-ray or neutron d i f f r a c t i o n data to z e o l i t e structure determination ( 2 0 ) , and STEM, w h i c h p r o v i d e s a t o m i c r e s o l u t i o n o f t h e c r y s t a l s t r u c t u r e and i t s c h e m i c a l c o m p o s i t i o n ( 2 1 ) , t o name j u s t a few. E q u a l l y s i g n i f i c a n t i s the development of a v a r i e t y o f c a t a l y t i c d i a g n o s t i c t o o l s w h i c h complement t h e p h y s i c a l c h e m i c a l c h a r a c t e r i z a t i o n t o o l s and provide a l i n k t o the r e a l world of i n d u s t r i a l catalysis. On t h e o t h e r hand, o u r knowledge o f c o n f i g u r a t i o n a l d i f f u s i o n i n z e o l i t e s i s f a r from b e i n g adequate. W h i l e F i c k ' s law on d i f f u s i o n has b e e n commonly u s e d t o o b t a i n d i f f u s i o n c o e f f i c i e n t s i n z e o l i t e s , t h e r e i s e x p e r i m e n t a l d a t a s u c h as t h e window o r c a g e e f f e c t o b s e r v e d i n e r i o n i t e w h i c h c a n n o t be i n t e r p r e t e d by s u c h e q u a t i o n s . D a t a on d i f f u s i o n o f high molecular weight molecules i n z e o l i t e s are almost nonexistent. D i s c r e p a n c i e s a l s o remain u n r e s o l v e d between d i f f u s i o n c o e f f i c i e n t s d e t e r m i n e d by NMR and uptake d a t a (22-23). N e e d l e s s t o s a y , much r e m a i n s t o be i n v e s t i g a t e d , b o t h i n t h e o r y (24-25) and i n e x p e r i m e n t a l measurement ( 2 6 ) . Catalytic

acidity

When z e o l i t e s were f i r s t shown t o have a c i d i t y f o r c a t a l y t i c c o n v e r s i o n n e a r l y 30 y e a r s ago, we were


472


f i l l e d with the e x p e c t a t i o n t h a t these porous c r y s t a l l i n e m a t e r i a l s o f h i g h s u r f a c e a r e a would p r o v i d e u s w i t h t h e o p p o r t u n i t y t o work w i t h w e l l d e f i n e d p o r e s o f known d i m e n s i o n s and a c t i v e s i t e s , w h i c h c o u l d be r e l a t e d t o t h e s t r u c t u r e o f t h e c r y s t a l . T h i s e x p e c t a t i o n has been o n l y p a r t i a l l y r e a l i z e d . As we showed many y e a r s ago, t h e p r o t o n i c s i t e s a s s o c i a t e d w i t h t h e framework aluminum c a n have a c i d a c t i v i t y many o r d e r s o f m a g n i t u d e h i g h e r t h a n t h a t o f t h e amorphous c a t a l y s t o f s i m i l a r aluminum c o n c e n t r a t i o n . But t h i s s h o u l d n o t be c o n s t r u e d a s an i n d i c a t i o n t h a t t h e c o r r e l a t i o n between s t r u c t u r e a n d a c t i v i t y i s completely understood. In fact, there i s s t i l l disagreement as t o t h e nature o f t h e a c i d s i t e i n d i f f e r e n t c h e m i c a l environments and d i f f e r e n t s t r u c t u r a l c o n f i g u r a t i o n s . Questions such as t h e r e l a t i o n s h i p between s i t e d e n s i t y a n d s i t e s t r e n g t h , and t h e n a t u r e o f d e f e c t s i t e s a n d a c t i v a t e d s i t e s (27) remain unresolved. In a d d i t i o n , the s u b s t i t u t i o n of a d d i t i o n a l e l e m e n t s , s u c h a s Ga, Ge, Β , P, e t c . , adds t o t h e c o m p l e x i t y o f t h e system, which i s a l s o f a r from b e i n g completely understood. B u t I b e l i e v e t h a t t h e most i m p o r t a n t c h a l l e n g e a t hand i s t o d e v i s e r a p i d and r e l i a b l e screening t e s t s t o i d e n t i f y the p r a c t i c a l u t i l i t y of t h i s large variety of catalysts. Industrial applications P e r h a p s f o r o b v i o u s r e a s o n s , most o f t h e c u r r e n t c o m m e r c i a l p r o c e s s e s u s i n g shape s e l e c t i v e c a t a l y s t s a r e i n t h e p e t r o l e u m and p e t r o c h e m i c a l i n d u s t r i e s . These p r o c e s s e s a l s o l a r g e l y f a l l i n t o t h e c a t e g o r y o f hydrocarbon c o n v e r s i o n o r c o n v e r s i o n o f nonhydrocarbons t o hydrocarbons over a c i d c a t a l y s t s . They include the r e a c t i o n s of o l e f i n s , p a r a f f i n s , aromatics and t h e i r m i x t u r e s i n t h e p r o d u c t i o n o f h i g h o c t a n e gasoline, high quality diesel, j e t f u e l , d i s t i l l a t e f u e l s and l u b r i c a n t s . T a b l e 1 shows a p a r t i a l l i s t o f these processes. The b e n e f i t s o f shape s e l e c t i v i t y c a n be d i s c u s s e d i n t e r m s o f t a n g i b l e g o a l s o f [1] r e d u c i n g t h e c o s t o f p r o d u c t i o n , [2] i m p r o v i n g t h e q u a l i t y o f t h e p r o d u c t , [3] i n c r e a s i n g t h e s u p p l y o f p r o d u c t f r o m u n c o n v e n t i o n a l f e e d s t o c k s a n d [4] c r e a t i n g t o t a l l y new products. The o c t a n e b o o s t i n g p r o c e s s e s a l l o w u s t o r e d u c e c o s t by i n c r e a s i n g y i e l d w i t h o u t s a c r i f i c i n g p r o d u c t quality. To r e d u c e c o s t , a new c a t a l y t i c d e w a x i n g p r o c e s s r e p l a c e s an e x p e n s i v e n o n c a t a l y t i c p r o c e s s . C a t a l y t i c d e w a x i n g d o e s n o t have t h e t e m p e r a t u r e l i m i t a t i o n o f a s o l v e n t dewaxing p r o c e s s . Thus, i t c r e a t e s a new c l a s s o f s u p e r - l o w f r e e z e p o i n t o r p o u r p o i n t p r o d u c t s f o r low t e m p e r a t u r e a p p l i c a t i o n s . The


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Shape-Selective Catalysis at the SO- Year Mark

Table 1 Processes U t i l i z i n g Catalysts

Shape S e l e c t i v e

473

Zeolite

S e l e c t o f o r m i n g (28-29) Octane b o o s t i n g M-Forming (30) Octane b o o s t i n g C a t a l y t i c c r a c k i n g (31-32-33-34-35) Octane b o o s t i n g MDDW (36-37-38-39-40) D i s t i l l a t e dewaxing MLDW (41-42) Lube dewaxing M2-Forming (43) Gas t o a r o m a t i c s C y c l a r (44-45) Gas t o A r o m a t i c s MOGD (46-47-48) Light olefins t o gasoline and d i s t i l l a t e MTG (49-50-51-52) Methanol t o g a s o l i n e MTO (53-54) Methanol t o l i g h t o l e f i n s MVPI, MLPI, MHTI (15-55) Xylene i s o m e r i z a t i o n MTDP (15) Toluene d i s p r o p o r t i o n a t i o n MBB (56) Ethylbenzene synthesis P a r a - s e l e c t i v e r e a c t i o n s (57-58-59) p-Xylene s y n t h e s i s p-ethyltoluene synthesis a b i l i t y t o produce f u e l s and c h e m i c a l s from u n c o n v e n t i o n a l f e e d s t o c k s by shape s e l e c t i v e c a t a l y s t s i s e x e m p l i f i e d by a r o m a t i z a t i o n o f l i g h t g a s e s , p r o d u c t i o n o f g a s o l i n e and d i s t i l l a t e from l i g h t o l e f i n s , and p r o d u c t i o n o f l i g h t o l e f i n s and g a s o l i n e from oxygenates, such as methanol. In the p e t r o c h e m i c a l a r e a , t h e r e a r e a number o f p r o c e s s e s i n v o l v i n g the p r o d u c t i o n o f aromatics. However, t h e r e i s l i t t l e d o u b t t h a t t h e a p p l i c a t i o n o f shape s e l e c t i v e c a t a l y s i s w i l l be extended from hydrocarbons t o the c o n v e r s i o n o f nonhydrocarbons and from a c i d c a t a l y s i s t o metal c a t a l y z e d and b i - f u n c t i o n a l c a t a l y s i s . A c u r s o r y l o o k a t t h e p a t e n t l i t e r a t u r e shows t h a t , f o r example, t h e d o u b l e bond o f u n s a t u r a t e d a l d e h y d e s a n d k e t o n e s c a n be i s o m e r i z e d o v e r l o w a c i d i t y medium p o r e z e o l i t e s w i t h o u t c l e a v i n g t h e c a r b o n y l g r o u p , a n d a l d e h y d e s a n d k e t o n e s c a n be i n t e r c o n v e r t e d by s k e l e t a l i s o m e r i z a t i o n (60-61). In s p i t e o f t h e f a c t t h a t a c i d s i t e s are prone t o be p o i s o n e d b y b a s i c n i t r o g e n compounds a n d p h e n o l s , n i t r o g e n compounds s u c h a s a m i n e s , p y r i d i n e s , a n i l i n e s , n i t r i l e s a n d p h e n o l s have been s y n t h e s i z e d w i t h medium pore z e o l i t e s w i t h the d e s i r e d s e l e c t i v i t y (62-63). Aromatic a l k y l a t i o n r e a c t i o n s which l e d t o a number o f p a r a - s e l e c t i v e p r o d u c t s have b e e n d u p l i c a t e d on p h e n o l s a n d t h i o p h e n e s (64-65-66-67). So have h a l o g e n a t i o n and n i t r a t i o n r e a c t i o n s (68-69). T h e r e f o r e , we a r e n o t o n l y a d d r e s s i n g t h e i s s u e o f p r o v i d i n g improved c a t a l y s t s f o r e x i s t i n g p r o c e s s technology, b u t a l s o e x p e c t i n g the c r e a t i o n o f t o t a l l y new p r o c e s s e s a n d new p r o d u c t s h e r e t o f o r e n o n - e x i s t e n t .


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25, 1988


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