Heterogeneous Catalysis - ACS Publications - American Chemical


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35 Frank G. Ciapetta—Pioneer in Catalytic Chemistry

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W. P. HETTINGER, JR. Ashland Petroleum Company, Ashland, KY 41101 Frank G. Ciapetta was born in Philadelphia in 1915. He earned his B.A. in Chemistry at Temple University in 1937, his M.A. in 1939, and his Ph.D. in 1947 from the University of Pennsylvania. His career involved responsible positions with Atlantic Refining Company, Socony-Vacuum and the Davison Division of W. R. Grace & Co. and endeavors including research involving homogeneous c a t a l y s i s , the discovery of a new general class isomerization catalyst and concepts of dual-size catalysis. During later years, efforts in developing a reforming catalyst making possible the Atlantic "Catforming Process" culminated in his receiving in 1955 the Precision S c i e n t i f i c Company Award of the American Chemical Society. In every phase of human a c t i v i t y - business, industry, technology, science, p o l i t i c s , law, medicine, the arts, athletics - there are "real pros." These are the stand-outs who have won the admiration and respect of their most important group of c r i t i c s - their peers. In c a t a l y s i s , "real pro" is an appelation that f i t s Dr. Frank G. Ciapetta. Frank was born in Philadelphia in 1915. With the aid of a senatorial scholarship, he enrolled at Temple University where he received a B.A. in Chemistry in 1937 and an M.A. in 1939. Upon graduation, he started work as a laboratory assistant in Research and Development Department of Atlantic Refining. At the same time, he began graduate study at the University of Pennsylvania and was awarded a Ph.D. in 1947; a remarkable achievement in i t s own right and a tribute to his dedication to science. Homogeneous catalysis was the subject of both his M.A. and his Ph.D. theses. Figure #1 is a picture of Frank taken in 1947 just after graduation. 0097-6156/83/0222-0505$06.00/0 © 1983 American Chemical Society Davis and Hettinger; Heterogeneous Catalysis ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

HETEROGENEOUS CATALYSIS

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F i g u r e 1 . A p h o t o g r a p h o f F r a n k G. C i a p e t t a t a k e n i n 1947 a f t e r h i s g r a d u a t i o n from the U n i v e r s i t y of P e n n s y l v a n i a .

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In 1 9 4 8 , he was p l a c e d i n c h a r g e o f A t l a n t i c ' s c a t a l y t i c p r o c e s s group and i n 1950 was made p r i n c i p a l c h e m i s t . There, d i s c o v e r y o f a new g e n e r a l c l a s s o f i s o m e r i z a t i o n c a t a l y s t s , c o n s i s t i n g of a hydrogenation-dehydrogenation a g e n t s u c h as n i c k e l o r p l a t i n u m , i n c o m b i n a t i o n w i t h an a c i d i c c r a c k i n g c a t a l y s t s u c h as s i l i c a - a l u m i n a , became h i s m a j o r c o n t r i b u t i o n . These c a t a l y s t s p o s s e s s e d h i g h a c t i v i t y and s e l e c t i v i t y f o r t h e i s o m e r i z a t i o n of unsaturated hydrocarbons. T h i s most i m p o r t a n t c o n t r i b u t i o n to c a t a l y s t s occurred i n the l a t e 4 0 ' s at A t l a n t i c R e f i n i n g Company R e s e a r c h w h i l e he was w o r k i n g on i s o m e r i z a t i o n o f normal p a r a f f i n s . A t t h a t t i m e , unbeknown t o e a c h o t h e r , D r . V l a d m i r H a e n s e l was a l s o i n v o l v e d i n h i s work on p l a t i n u m on a l u m i n a r e f o r m i n g c a t a l y s t promoted w i t h f l u o r i d e , w h i c h work u l t i m a t e l y l e d t o t h e p l a t f o r m i n g p r o c e s s o f UOP and f o r w h i c h work D r . H a e n s e l u l t i m a t e l y r e c e i v e d t h e P r e s i d e n t ' s Medal o f S c i e n c e . Unbeknown t o e i t h e r man, F r a n k i n d e p e n d e n t l y began t o e x p l o r e t h e use o f n i c k e l and p l a t i n u m s u p p o r t e d on s i l i c a - a l u m i n a and d i s c o v e r e d t h a t by t h e p r o p e r t r e a t m e n t o f s i l i c a - a l u m i n a c a t a l y s t by h i g h t e m p e r a t u r e steam t r e a t m e n t , he c o u l d c o u p l e o r h a r n e s s t h e a c t i v i t y o f n i c k e l and l a t e r p l a t i n u m t o t h e a c i d i t y o f t h e c a t a l y s t so as t o p r o v i d e a v e r y i n t e r e s t i n g material f o r reforming of hydrocarbons. T h i s work e v e n t u a l l y l e d to the c o m m e r c i a l i z a t i o n of the "Catforming P r o c e s s " of Atlantic. He l a t e r went on t o e x p l o r e t h i s r e a c t i o n i n g r e a t d e t a i l and p u b l i s h e d a number o f i m p o r t a n t p a p e r s r e l a t e d t o t h i s work. H i s work and t h a t o f D r . H a e n s e l l e d t o t h e r e a l i z a t i o n , and l a t e r p r o o f by o t h e r r e s e a r c h e r s as w e l l , t h a t two d i f f e r e n t c a t a l y t i c s i t e s were r e q u i r e d i n i s o m e r i z a t i o n namely b o t h h y d r o g e n a t i o n - d e h y d r o g e n a t i o n s i t e s and a c i d i c sites. T h i s work u l t i m a t e l y l e d t o t h e c o n c e p t o f d u a l - s i t e catalysis. S i n c e t h a t t i m e , d u a l - s i t e c a t a l y s i s has been s t u d i e d i n g r e a t d e t a i l by many c a t a l y s t i n v e s t i g a t o r s a r o u n d the w o r l d . P r e v i o u s knowledge o f t h e i s o m e r i z a t i o n o f h y d r o c a r b o n s had been l i m i t e d p r i m a r i l y t o l o w t e m p e r a t u r e s and l o w m o l e c u l a r w e i g h t h y d r o c a r b o n s , u s i n g c a t a l y s t s s u c h as aluminum c h l o r i d e . W i t h t h e d u a l - f u n c t i o n a l c a t a l y s t s , i t was now p o s s i b l e t o i s o m e r i z e h y d r o c a r b o n s o f much h i g h e r m o l e c u l a r w e i g h t and a t considerably higher temperatures. In 1 9 5 1 , F r a n k j o i n e d t h e R e s e a r c h and D e v e l o p m e n t D e p a r t m e n t o f Socony-Vacuum and became R e s e a r c h A s s o c i a t e i n change o f c a t a l y s t r e s e a r c h . At Socony-Vacuum, Ciapetta's r e s e a r c h was f o c u s e d on t h e c h e m i c a l and p h y s i c a l f a c t o r s t h a t

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i n f l u e n c e t h e a c t i v i t y and s e l e c t i v i t y o f m e t a l - a c i d i c o x i d e catalysts. His study of i s o m e r i z a t i o n - d e h y d r o g e n a t i o n c a t a l y s t s l e d t o Socony-Vacuum's i n t r o d u c t i o n o f the S o v a - F o r m i n g P r o c e s s used c o m m e r c i a l l y i n s e v e r a l r e f i n e r i e s . T h i s was a most s u c c e s s f u l e i g h t - y e a r r e s e a r c h campaign on the a p p l i c a t i o n s o f c a t a l y s i s to hydrocarbon c h e m i s t r y , h a l f of w h i c h was s p e n t a t A t l a n t i c and h a l f a t Socony as a R e s e a r c h Associate. H i s m a j o r a r e a o f a c t i v i t y w i t h b o t h o i l companies was i n r e f i n e r y c a t a l y t i c p r o c e s s e s - c r a c k i n g , r e f o r m i n g , h y d r o c r a c k i n g , i s o m e r i z a t i o n and a l k y l a t i o n , and p e t r o l e u m c o n v e r s i o n g e n e r a l l y , and w i t h a l l t y p e s o f bed c o n c e p t s f i x e d , m o v i n g , and f l u i d i z e d . During h i s l a t t e r years at A t l a n t i c , he worked c l o s e l y w i t h D a v i s o n s c i e n t i s t s on d e v e l o p i n g t h e r e f o r m i n g c a t a l y s t t h a t s u b s e q u e n t l y made p o s s i b l e the A t l a n t i c "Catforming P r o c e s s . " T h i s work c u l m i n a t e d i n h i s r e c e i v i n g t h e c o v e t e d P r e c i s i o n S c i e n t i f i c Company Award o f t h e A m e r i c a n C h e m i c a l S o c i e t y i n Petroleum Chemistry i n 1955. F i g u r e #2 i s f r o m t h e f r o n t page o f t h e C h e m i c a l and E n g i n e e r i n g News, A p r i l 1 1 , 1 9 5 5 , when Frank r e c e i v e d t h e P r e c i s i o n S c i e n t i f i c Award. F o l l o w i n g i s an a b s t r a c t o f h i s a d d r e s s w h i c h was p r e s e n t e d b e f o r e t h e D i v i s i o n o f P e t r o l e u m Chemistry a t t h e American Chemical S o c i e t y Meeting i n C i n c i n n a t i , A p r i l 4 - 7 , 1955.

THE REACTIONS OF PURE HYDROCARBONS IN THE OF DUAL-FUNCTIONAL CATALYSTS

PRESENCE

BY FRANK G. CIAPETTA (A DIVISION OF SOCONY-VACUUM OIL COMPANY, I N C . ) RESEARCH AND DEVELOPMENT DEPARTMENT PAULSBORO, NEW JERSEY A major f a c t o r i n the r a p i d commercial u t i l i z a t i o n of c a t a l y t i c reforming processing f o r upg r a d i n g l o w o c t a n e n a p h t h a s , and t h e p r o d u c t i o n o f a r o m a t i c s f r o m p e t r o l e u m s o u r c e s , has been t h e d e v e l o p m e n t o f more a c t i v e and s e l e c t i v e d u a l functional catalysts. These c a t a l y s t s c o n t a i n a very a c t i v e hydrogenation-dehydrogenation agent such as p l a t i n u m , i n c o m b i n a t i o n w i t h an a c i d i c o x i d e s u p p o r t such as a l u m i n a o r s i l i c a - a l u m i n a .

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F i g u r e 2 . F r a n k C i a p e t t a i n 1955 r e c e i v i n g t h e P r e c i s i o n S c i e n t i f i c Award o f t h e A m e r i c a n C h e m i c a l S o c i e t y i n P e t r o l e u m C h e m i s t r y .

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A t hydrogen p r e s s u r e s o f a p p r o x i m a t e l y 500 p . s . i . g . , these c a t a l y s t s maintain t h e i r a c t i v i t y f o r r e forming v i r g i n naphthas f o r long p e r i o d s of t i m e . An e x t e n s i v e s t u d y o f t h e r e a c t i o n s o f p u r e hydrocarbons, including alkanes, c y c l o a l k a n e s , a l k e n e s and a r o m a t i c s has been made i n t h e p r e s e n c e of hydrogen, these c a t a l y s t s are a c t i v e f o r (1) i s o m e r i z a t i o n o f a l k a n e s , c y c l o a l k a n e s , and a l k y l a r o m a t i c s , (2) h y d r o i s o m e r i z a t i o n o f a l k y l c y c l o p e n t a n e s t o a r o m a t i c s , and (4) d e h y d r o g e n a t i o n o f a l k a n e s and c y c l o h e x a n e s t o a r o m a t i c s . The a c t i v i t y and s e l e c t i v i t y o f t h e s e c a t a l y s t s a r e dependent p r i m a r i l y on (1) t h e hydrogenation-dehydrogenation component used and i t s c o n c e n t r a t i o n , (2) t h e a c i d i t y o f t h e o x i d e s u p p o r t , and (3) t h e r e a c t i o n c o n d i t i o n s . The e f f e c t o f t h e s e f a c t o r s on t h e c o n v e r s i o n o f p u r e h y d r o c a r b o n s as w e l l as t h e mechanism o f t h e s e r e a c t i o n s w i l l be d i s c u s s e d . Due t o t h e i r h i g h a c t i v i t y and s e l e c t i v i t y o f i s o m e r i z a t i o n and d e h y d r o g e n a t i o n r e a c t i o n s , d u a l f u n c t i o n a l c a t a l y s t s produce l a r g e q u a n t i t i e s of high p u r i t y hydrogen as a b y - p r o d u c t i n t h e r e f o r m i n g o f naphthas. U t i l i z a t i o n of t h i s hydrogen f o r commercial p r o c e s s e s s u c h as h y d r o r e f i n i n g o f c r a c k e d n a p h t h a s , d i s t i l l a t e f u e l o i l s and l u b e o i l s , and ammonia p r o d u c t i o n i s r a p i d l y expanding throughout the petroleum industry. A t t h a t t i m e he a l s o made t h e f o l l o w i n g o b s e r v a t i o n s and comments w h i c h were q u i t e p e r c e p t i v e . " D u r i n g t h e p a s t few y e a r s o u r p e t r o l e u m i n d u s t r y has r a p i d l y i n c r e a s e d t h e o c t a n e number o f i t s t o t a l g a s o l i n e p o o l by a d d i n g c a t a l y t i c r e f o r m i n g p r o c e s s e s t o upgrade t h e q u a l i t y o f s t r a i g h t - r u n and t h e r m a l l y cracked naphthas. R e f o r m i n g c a p a c i t y has grown a t a p h e n o m e n a l , r a t e f r o m l e s s t h a n 8 0 , 0 0 0 b a r r e l s p e r day i n 1950 to 200,000 b a r r e l s at the b e g i n n i n g of 1955. By t h e end o f t h i s y e a r , r e f o r m i n g c a p a c i t y w i l l pass the 1 m i l l i o n b a r r e l - p e r - d a y m a r k , an amount a l m o s t e q u i v a l e n t t o t h e volume o f s t r a i g h t - r u n naphtha now p r o d u c e d . L a r g e amounts o f h i g h p u r i t y hydrogen (80 t o 95%) a r e obtained during reforming. I f we assume 500 c u b i c f e e t o f hydrogen p e r b a r r e l o f s t r a i g h t - r u n n a p h t h a as an a v e r a g e y i e l d t h e n r e f i n e r i e s w i l l be t u r n i n g o u t 500 m i l l i o n c u b i c f e e t o f hydrogen p e r day by t h e end o f 1 9 5 5 . Many companies a r e

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i n s t a l l i n g new p r o c e s s e s t o u t i l i z e t h i s o u t p u t ; t o r e d u c e s u l f u r and u n s a t u r a t i o n i n r e f o r m e r c h a r g e s t o c k s ; t o r e d u c e s u l f u r and m e r c a p t a n c o n t e n t s , and t o i m p r o v e t h e c o l o r , s t o r a g e a b i l i t y , and c o m b u s t i o n c h a r a c t e r i s t i c s o f l i g h t d i s t i l l a t e f u e l o i l ; t o r e d u c e s u l f u r and c a r b o n r e s i d u e , and t o i m p r o v e t h e c o l o r , o d o r , and s t a b i l i t y o f l u b e o i l s . By y e a r - e n d a l m o s t 11% o f t h e ammonia p r o d u c e d i n t h e U n i t e d S t a t e s w i l l u t i l i z e hydrogen from c a t a l y t i c r e f o r m i n g . "

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In 1 9 5 5 , he began h i s a s s o c i a t i o n w i t h D a v i s o n ; f i r s t a t t h e R e s e a r c h F a c i l i t i e s a t C u r t i s B a y , M a r y l a n d , and l a t e r i n 1958 a t t h e W a s h i n g t o n R e s e a r c h C e n t e r n e a r C l a r k s v i l l e , Maryland. F r a n k j o i n e d W. R. G r a c e & Company as R e s e a r c h D i r e c t o r of the Davison Chemical D i v i s i o n . F r a n k ' s e n t h u s i a s m f o r , and s u c c e s s i n , m a t t e r s c a t a l y t i c c o n t i n u e d a t D a v i s o n and l e d t o some f u r t h e r r e m a r k a b l e d e v e l o p m e n t s i n c r a c k i n g , e s p e c i a l l y t h e new m o l e c u l a r s i e v e b a s e d c a t a l y s t s w h i c h a p p e a r e d i n t h e e a r l y 6 0 ' s , as w e l l as a u t o e x h a u s t and p o l y m e r i z a t i o n c a t a l y s t s . In 1968 he was named V i c e P r e s i d e n t f o r R e s e a r c h , D a v i s o n D i v i s i o n o f W. R. G r a c e i n r e c o g n i t i o n o f h i s many c o n t r i b u t i o n s n o t o n l y t o c a t a l y s i s b u t t o D a v i s o n as w e l l . In t h o s e l a t e r y e a r s he saw t h e d e d i c a t i o n o f a r e s e a r c h c e n t e r devoted to c a t a l y s i s at the C l a r k s v i l l e Research L a b o r a t o r i e s in Maryland. For the f i r s t time a l a r g e r e s e a r c h f a c i l i t y d e v o t e d t o c a t a l y s t r e s e a r c h was c o n s t r u c t e d i n o r d e r t o s u p p o r t work i n i n d u s t r i a l c a t a l y s t r e s e a r c h . Many p a t e n t s , p u b l i c a t i o n s , s p e c i a l h o n o r s and awards came to him. He was t h e a u t h o r o f more t h a n 27 s c i e n t i f i c p u b l i c a t i o n s and h i s name a p p e a r s on 43 U n i t e d S t a t e s and many f o r e i g n p a t e n t s on c r a c k i n g , r e f o r m i n g , and h y d r o c r a c k i n g c a t a l y s t s ; on r e f o r m i n g and h y d r o c r a c k i n g c a t a l y t i c p r o c e s s e s ; and on o x i d a t i o n c a t a l y s t s f o r e x h a u s t g a s e s . The e n t i r e f i e l d o f c a t a l y s i s was g r e a t l y e n r i c h e d by h i s many-faceted c o n t r i b u t i o n s . In a d d i t i o n t o h i s a c t i v e memberships i n t h e A m e r i c a n C h e m i c a l S o c i e t y , t h e A m e r i c a n P e t r o l e u m I n s t i t u t e , and t h e A m e r i c a n A s s o c i a t i o n f o r t h e Advancement o f S c i e n c e , he d e v o t e d many h o u r s t o t h e t e c h n i c a l g r o u p s c o n c e r n e d s p e c i f i c a l l y w i t h c a t a l y s i s and p a r t i c i p a t e d a c t i v e l y i n many r e l a t e d s c i e n t i f i c and t e c h n i c a l organizations. He was t h e f i r s t p r e s i d e n t and a f o u n d i n g

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C a t a l y s i s S o c i e t y , an e v o l u t i o n a r y d e v e l o p m e n t f r o m what was o r i g i n a l l y t h e I n t e r n a t i o n a l C o n g r e s s on C a t a l y s i s , I n c . In 1949 a group o f P h i l a d e l p h i a c a t a l y t i c c h e m i s t s ( i n c l u d i n g Dr. C i a p e t t a ) organized the f i r s t c a t a l y s t c l u b , the C a t a l y s i s C l u b o f P h i l a d e l p h i a . T h e n , a group o f t h e s e men, a l s o i n c l u d i n g D r . C i a p e t t a , o r g a n i z e d and h e l d , i n 1 9 5 6 , t h e w o r l d ' s f i r s t I n t e r n a t i o n a l C o n g r e s s on C a t l a y s i s . Some 800 a c a d e m i c and i n d u s t r i a l c a t a l y t i c e x p e r t s came f r o m 17 c o u n t r i e s to P h i l a d e l p h i a f o r the meetings. In 1960 t h e l o c a l e o f t h e m e e t i n g moved t o P a r i s ; and t o Amsterdam i n 1 9 6 4 , each C o n g r e s s showing s t r o n g g a i n s i n attendance. The C o n g r e s s i s now o r g a n i z e d as a r e c o g n i z e d i n t e r n a t i o n a l group o f some 14 n a t i o n s ( u n d e r I U P A C ) . Frank was p r e s i d e n t o f t h e I n t e r n a t i o n a l C o n g r e s s on C a t a l y s i s and Chairman o f t h e P e t r o l e u m R e s e a r c h Fund A d v i s o r y B o a r d when he died. One o f D r . C i a p e t t a ' s l a s t a c c o l a d e s was h i s s e l e c t i o n t o p r e s e n t t h e m a j o r r e v i e w p a p e r on t r e n d s i n p e t r o l e u m r e f i n i n g c a t a l y s i s a t the Seventh World Petroleum Congress i n Mexico C i t y i n 1967. T h i s was one o f 18 p a p e r s c o v e r i n g m a j o r p h a s e s o f p e t r o l e u m t e c h n o l o g y , d e l i v e r e d by l e a d i n g s c i e n t i s t s f r o m a l l over the w o r l d . Frank was one o f o n l y f o u r A m e r i c a n s on the program. T h i s was a n a t u r a l c o n s e q u e n c e o f a v i r t u a l l i f e t i m e d e v o t e d t o work i n t h e f i e l d o f c a t a l y s i s a c a d e m i c a l l y , i n d u s t r i a l l y , and i n p r o f e s s i o n a l and s c i e n t i f i c groups. A q u i e t , unassuming man, he was r e s p e c t e d by a l l who knew him. He was l o v e d by many, b o t h f o r h i s p r o f e s s i o n a l a c t i v i t i e s as w e l l as f o r h i s warm, f r i e n d l y and c h a r m i n g personality. He was a good f r i e n d and a warm i n d i v i d u a l t o know and t o be a s s o c i a t e d w i t h . He had a l o v e o f l i f e and t h e f u n o f f r i e n d s h i p as w e l l as s p o r t i n g a c t i v i t i e s . In h i s e a r l i e r d a y s , he was an e n t h u s i a s t i c t e n n i s p l a y e r and i n l a t e r y e a r s t r a n s f e r r e d t h a t e n t h u s i a s m f r o m t e n n i s t o g o l f ; w h i c h he e n t e r e d i n t o w i t h t h e same e n t h u s i a s m t h a t he had shown f o r a l l of h i s p r o f e s s i o n a l i n t e r e s t s . F i g u r e #3 shows F r a n k p a r t i c i p a t i n g i n h i s f a v o r i t e s p o r t a t an a n n u a l D a v i s o n g o l f outing. F r a n k was a l s o a g r e a t f a m i l y man and v e r y proud o f h i s son and d a u g h t e r . He was e s p e c i a l l y proud and t r a v e l e d e x t e n s i v e l y w i t h h i s sweet and c h a r m i n g w i f e , C a r o l y n . Wherever t h e r e was a p r o f e s s i o n a l c a t a l y s i s m e e t i n g , Frank w o u l d be i n a t t e n d a n c e and C a r o l y n was a l m o s t a l w a y s t h e r e t o add t o t h e e n j o y m e n t o f

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Frank G. Ciapetta

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35.

Figure 3.

Frank C i a p e t t a e n j o y i n g the annual

Davison g o l f

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h i s company. S h e , t o o , became w e l l known t h r o u g h o u t t h e c a t a l y s t r e s e a r c h w o r l d and was a l w a y s a c h a r m i n g h o s t e s s .

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On F e b r u a r y 7 , 1 9 7 2 , on a h o t summer day (summer f o r A r g e n t i n a ) , w h i l e a t t e n d i n g a barbecue p i c n i c i n the hot A r g e n t i n a sun where he was t o u r i n g and l e c t u r i n g , F r a n k e x p e r i e n c e d an u n p l e a s a n t f e e l i n g and l a t e t h a t a f t e r n o o n and succumbed t o a h e a r t a t t a c k . He was i n A r g e n t i n a a t t h a t t i m e l e c t u r i n g on h i s f a v o r i t e s u b j e c t , c a t a l y s i s , and as u s u a l was h a v i n g a tremendous t i m e t r a v e l i n g . F r a n k l o v e d t o t r a v e l as did Carolyn. F o r t u n a t e l y s h e was a t h i s s i d e when t h i s occurred. A l l o f h i s f r i e n d s and a s s o c i a t e s w i l l l o n g remember, w i t h warmest f e e l i n g s , b e i n g a s s o c i a t e d w i t h him and w i s h t h a t he were h e r e t o d a y t o l e n d h i s c h a r m , w a r m t h , w i t and e n t h u s i a s m t o t h i s symposium. We a l l know we have l o s t a w o n d e r f u l friend. Attached i s a l i s t

of Frank's

p a t e n t s and p u b l i c a t i o n s .

Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

Tomlinson, Hazel M . ; Ciapetta, Frank G. Ind. Eng. Chem. Anal. E d . , 1941, 13, 539-540. Ciapetta, Frank G. Ind. End. Chem., 1945, 37, 1210-1216. Leum, Leonard M.; Ciapetta, Frank G. U.S. Patent 2 390 951, 1945. Ciapetta, Frank G. Ph.D. Dissertation, University of Pennsylvania, Philadelphia, P a . , 1947. Ciapetta, Frank G. U.S. Patent 2 430 803, 1947. Ciapetta, Frank G. U.S. Patent 2 434 833, 1948. Ciapetta, Frank G . ; Kilpatrick, Martin. J . Am. Chem. Soc., 1948, 70, 639-646. Macuga, Stephen J.; Ciapetta, Frank G . ; Heiliqmann, Randall G. U.S. Patent 2 447 762, 1948. Ciapetta, Frank G . ; Macuga, Stephen J.; Leum, Leonard M. Anal. Chem., 1948, 20, 699-704. Ciapetta, Frank G . ; Macuga, Stephen J.; Leum, Leonard M. Ind. Eng. Chem., 1948, 40, 2091-2099. Ciapetta, Frank G. U.S. Patent 2550 531, 1951. Ciapetta, Frank G . ; Tomlinson, H.M. J. Phys. Colloid Chem., 1951, 55, 429-439. Ciapetta, Frank G . ; P i t t s , Paul M . ; Leum, Leonard M. Adv. Chem. Ser., 1951, 5, 76-82. Ciapetta, Frank G . ; Buck, William H. U.S. Patent 2 589 189, 1952. Ciapetta, Frank G . ; Hunter, James B. Ind. Eng. Chem., 1953, 45, 147-155.

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Ciapetta, Frank G . ; Hunter, James B. Ind. Eng. Chem., 1953, 45, 155-159. Ciapetta, Frank G. Ind. Eng. Chem., 1953, 45, 159-162. Ciapetta, Frank G. Ind. Eng. Chem., 1953, 45, 162-165. Ciapetta, Frank G. U.S. Patent 2 651 598, 1953. Ciapetta, Frank G . ; Plank, C. J. In "Catalysis 1, Fundamental Principles"; Ries, Herman E.; Reinhold: New York, 1954; Part 1, p. 315-352. Conner, J. E., Jr.; Ciapetta, Frank G . ; Leum, Leonard M.; Fowle, M. J. Ind. Eng. Chem., 1955, 47, 152-156. Ciapetta, Frank G. General Papers, ACS, Div. of Pet. Chem., 33, 167, 1955. Ciapetta, Frank G . ; Hunter, James B. U.S. Patent 2 721 226, 1955. Meisel, Seymour L; Koft, Emil Jr., Ciapetta, Frank G. Prepr., Div. Pet. Chem., Am. Chem. Soc., 1957, 2 (4), A45-A51. Baker, Richard W.; Ciapetta, Frank G . ; Dobres, Robert M. U.S. Patent 2 849 378, 1958. Ciapetta, Frank G . ; Dobres, Robert M.; Baker, R. W. In "Catalysis-Alkylation Isomerization, Polymerization, Cracking, and Hydroforming", Emmett, Paul H . , E d . , Reinhold: New York, 1958, Vol. 6, p. 495-692. Ciapetta, Frank G . ; Koft, Emil Jr.; Meisel, Seymour L. U.S. Patent 2 876 268, 1959. Myers, C. G . ; Sibbett, D. J.; Ciapetta, Frank G. J. Phys. Chem., 1959, 63, 1032-1041. Ciapetta, Frank G. U.S. Patent 2 914 461, 1959. Coonradt, Harry L.; Ciapetta, Frank G . ; Garwood, William E.; Leaman, W. K . ; Miale, J. N. Prepr., Div. Pet. Chem., Am. Chem. Soc., 1960, 5 (4), B35-B51. P i t t s , Paul M . , Jr.; Ciapetta, Frank G. U.S. Patent 2 942 041, 1960. Ciapetta, Frank G . ; Coonradt, Harry L.; Garwood, William E. U.S. Patent 2 945 800, 1960. Ciapetta, Frank G . ; Coonradt, Harry L.; Garwood, William E. U.S. Patent 2 945 802, 1960. Ciapetta, Frank G . ; Coonradt, Harry L.; Garwood, William E. U.S. Patent 2 945 805, 1960. Ciapetta, Frank G. U.S. Patent 2 945 806, 1960. Ciapetta, Frank G. Petro/Chem. Eng., 1961, 33 (5), C19-C31. Coonradt, Harry L.; Ciapetta, Frank G . ; Garwood, William E . ; Leaman, W. K . ; Miale, J . N . Ind. Eng. Chem., 1961, 53, 727-732. Ciapetta, Frank G . ; Coonradt, Harry L.; Garwood, William E. U.S. Patent 3 015 549, 1962. Ciapetta, Frank G . ; Coonradt, Harry L.; Garwood, William E. U.S. Patent 3 023 159, 1962.

17. 18. 19. 20.

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24.

25.

26.

27. 28. 29. 30.

31. 32. 33. 34. 35. 36. 37. 38. 39.

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40. Ciapetta, Frank G.; Coonradt, Harry L.; Garwood, William E. U.S. Patent 3 046 219, 1962. 41. Wilson, Charles P., Jr.; Ciapetta, Frank G.; Elston, James W. U.S. Patent 3 055 737, 1962. 42. Wilson, Charles P., Jr.; Ciapetta, Frank G.; Elston, James W. U.S. Patent 3 066 012, 1962. 43. Ciapetta, Frank G.; Coonradt, Harry L.; Garwood, William E. U.S. Patent 3 111 482, 1963. 44. Ciapetta, Frank G.; Coonradt, Harry L.; Garwood, William E. U.S. Patent 3 115 456, 1963. 45. Wilson, Charles P., Jr.; Jones, John B.; Ciapetta, Frank G. U.S. Patent 3 124 540, 1964. 46. Wilson, Charles P., Jr.; Ciapetta, Frank G.; Jones, John B. U.S. Patent 3 124 541, 1964. 47. Baker, R. W., Blazek, J. J.; Maher, P. K.; Ciapetta, Frank G.; Evans, R. E. The Oil and Gas Journal, 1964, 62 (18), 78-84. 48. Baker, R. W.; Ciapetta, Frank G. Proc. Am. Pet. Inst., Section III, 1964, 44, 452-461. 49. Ciapetta, Frank G.; Elston, James W., Jr.; Wilson, Charles P., Jr. U.S. Patent 3 129 189, 1964. 50. Wilson, Charles P., Jr.; Ciapetta, Frank G.; Elston, James W., Jr. U.S. Patent 3 131 156, 1964. 51. Ciapetta, Frank G.; Coonradt, Harrv L.; Garwood, William E. U.S. Patent 3 144 401, 1964. 52. Ciapetta, Frank G.; Coonradt, Harry L.; Garwood, William E. U.S. Patent 3 150 071, 1964. 53. Dobres, R. M.; Rheaume, Leo; Ciapetta, Frank G. Ind. Eng. Chem. Prod. Res. Dev., 1966, 5 (2), 174-182. 54. Ciapetta, Frank G.; Jones, John B.; wilson, Charles P., Jr. U.S. Patent 3 267 044, 1966. 55. Baker, Richard W.; Blazek, James J.; Ciapetta, Frank G. U.S. Patent 3 271 300, 1966. 56. Magee, John S.; Briggs, Warren S.; Ciapetta, Frank G. U.S. Patent 3 325 247, 1967. 57. Ciapetta, Frank G.; Henderson, Donald S. The Oil and Gas Journal, 1967, 65 (42), 88-93. 58. Henderson, DonaTd S.; Ciapetta, Frank G. Prepr., Div. Pet. Chem., Am. Chem. Soc., 1967, 12 (3), 83-99. 59. Carr, Brownell; Ciapetta, Frank G.; Wilson, Charles P., Jr. U.S. Patent 3 352 636, 1967. 60. Baker, Richard W.; Ciapetta, Frank G.; Wilson, Charles P., Jr. U.S. Patent 3 404 097, 1968. 61. Ciapetta, Frank G. Chem. Ind., 1969, 51, 1173-1183. 62. Baker, Richard W.; Ciapetta, Frank G.; Wilson, Charles P., Jr. U.S. Patent 3 425 956, 1969. 63. Baust, George Α.; Ciapetta, Frank G.; Henderson, Donald S. U.S. Patent 3 471 270, 1969. 64. Maqee, John S., Jr.; Surland, George J.; Briggs, Warren S.; Ciapetta, Frank G. U.S. Patent 3 501 418, 1970.

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65. Carr, Brownell; Ciapetta, Frank G.; Wilson, Charles P., Jr. U.S. Patent 3 520 654, 1970. 66. Ciapetta, Frank G.; Parthasarathy, R. U.S. Patent 3 557 199, 1971. 67. Ciapetta, Frank G. Catalysis Reviews, 1971, 5 (1), 67-158. 68. Parthasarathy, R.; Warthen, John L.; Ciapetta, Frank G. U.S. Patent 3 830 847, 1974. 69. Briggs, W.; Ciapetta, Frank G.; Warthen, John L. U.S. Patent 3 853 789, 1974. RECEIVED November 29, 1982

Davis and Hettinger; Heterogeneous Catalysis ACS Symposium Series; American Chemical Society: Washington, DC, 1983.