The Development of the Platforming ProcessâSome Personal and

11 The Development of the Platforming ProcessSome Personal and Catalytic Recollections VLADIMIR HAENSEL

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Downloaded by GEORGETOWN UNIV on October 6, 2016 | http://pubs.acs.org Publication Date: June 3, 1983 | doi: 10.1021/bk-1983-0222.ch011

University of Massachusetts, Amherst, MA 01103

An examination of one's career i n science and technology i s an i n t e r e s t i n g exercise. Despite a long passage of time, there are events that remain very clear i n one's memory bank. And yet, when people ask why or how or when did you think up a p a r t i c u l a r idea, one cannot put together a sequence i n either reasoning or time. Thus, i t appears that ideas germinate over a fairly long period of time and then they are given a push by c e r t a i n "gut feelings" which then propel the individual to design a set of experiments. Thus, i t i s d i f f i c u l t to r e c a l l s p e c i f i c sequences of the thinking process, but d e t a i l s of the experiments are very e a s i l y r e c a l l e d . One can also r e c a l l very well discussions which had an input on the d i r e c t i o n of work. Indeed, my c a t a l y t i c r e c o l lections are r e a l l y those of people and c a t a l y t i c events. My first introduction to c a t a l y t i c reforming was i n the summer of 1935. I had just graduated from Northwestern University and was to s t a r t a chemical engineering course at M . I . T . i n the fall. Through the e f f o r t s of Prof. V. N. I p a t i e f f , who was a great f r i e n d of my f a t h e r ' s , I got a summer job at UOP. I had worked there at no pay during previous summers to acquire experience, however, during the summer of 1935 I received $50 a month working as a technician i n the c a t a l y t i c reforming laboratory. In those days our usual catalyst was chromia on alumina which had just been discovered as a dehydrocyclization catalyst. The pressures were nearly atmospheric and no hydrogen was used. When my supervisor l e f t for vacation, Dr. Gustav Egloff came to the laboratory. To those of you who have heard of "Gasoline Gus" but have not met him, I s h a l l give you a short d e s c r i p t i o n . A short, wiry, 1

Retired from Universal Oil Products 0097-6156/83/0222-0141$06.00/0 © 1983 American Chemical Society

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


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dark complexioned i n d i v i d u a l , a champion w r e s t l e r i n h i s days a t Columbia, a p r o l i f i c i n v e n t o r , w i t h some t h r e e hundred p a t e n t s , and the author o f a number o f books and innumerable a r t i c l e s . He was one o f the few i n d i v i d u a l s who c o u l d e x p l a i n petroleum r e f i n i n g to a t a x i d r i v e r and u s u a l l y d i d . E g l o f f used t o come t o the UOP l a b o r a t o r i e s i n R i v e r s i d e a t f r e q u e n t intervals. On hot days, he used t o put dry i c e i n the h o l l o w o f h i s hat a p p a r e n t l y t o keep a " c o o l head". At v a r i o u s t e c h n i c a l meetings, he used t o appear d r e s s e d i n a l l s y n t h e t i c c l o t h i n g , and championed the c o n v e r s i o n of petroleum to a l l p o s s i b l e products. On t h a t day i n J u l y 1935, " G a s o l i n e Gus" i n d i c a ted t o me t h a t , a f t e r a l l , the main t r o u b l e w i t h c a t a l y t i c r e f o r m i n g , as we were d o i n g i t then, was the f o r m a t i o n o f carbon. Young and i n e x p e r i e n c e d as I was, I r e a l i z e d t h i s a l s o , but then came the bombshell: "You have about t h r e e weeks on your own — why don't you f i g u r e out a way o f d o i n g the r e a c t i o n w i t h o u t a l l t h i s carbon f o r m a t i o n ? " Frankly, I d i d not t h i n k i t was i m p o s s i b l e so I worked on i t and a t the end o f the t h r e e weeks t h e r e was a s i n g u l a r l a c k of s u c c e s s . To t h i s day, I do not know i f " G a s o l i n e Gus" was s e r i o u s about t h i s o r n o t . T h i s was my f i r s t brush with c a t a l y t i c reforming. Then came M.I.T. and i n 1937 I was h i r e d by UOP as a c h e m i c a l e n g i n e e r , working i n the p i l o t p l a n t s . In 1939 came an o p p o r t u n i t y t o work as an a s s i s t a n t to I p a t i e f f i n the newly e s t a b l i s h e d I p a t i e f f High P r e s s u r e Lab a t Northwestern and o b t a i n a Ph.D. degree a t the same time w h i l e s t i l l working a t UOP. In 1941 I r e t u r n e d f u l l time t o the UOP R i v e r s i d e Labora t o r i e s t o work f o r I p a t i e f f . The next f i v e y e a r s were most i n s t r u c t i v e not o n l y from the s t a n d p o i n t o f t e c h n i c a l growth, but a l s o working f o r a man who was one o f the g r e a t e s t i n the w o r l d o f c a t a l y s i s . In r e t r o s p e c t , the g r e a t n e s s was t h a t o f a simp l e man. He knew he was good and he d i d not have t o impress anyone. He was c o n f i d e n t because he knew c h e m i s t r y and was bound and determined t o l e a r n more. When I p a t i e f f f i r s t came t o t h i s c o u n t r y he was 62 years o l d . He knew v e r y l i t t l e E n g l i s h and the conv e r s a t i o n s w i t h h i s a s s o c i a t e s were most d i f f i c u l t , but c h e m i c a l p r o g r e s s , n e v e r t h e l e s s , was v e r y r a p i d , d e s p i t e many c o m i c a l s i t u a t i o n s t h a t a r o s e from the language d i f f e r e n c e s . I p a t i e f f became a U.S. c i t i z e n in 1935 and the judge asked him i f he attended church. I p a t i e f f s a i d "yes". The judge p e r s i s t e d : "Which church?" To which I p a t i e f f r e p l i e d : "Any



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church, God i s everywhere." A f t e r that r e p l y there were no more q u e s t i o n s . A c t u a l l y , I p a t i e f f was a v e r y devout person. He was a member o f the R u s s i a n Orthodox Church. U n f o r t u n a t e l y , the Russian church was m i l e s away and the s e r v i c e s t h e r e l a s t e d two hours and were not v e r y prompt. The p u n c t u a l and p r e c i s e I p a t i e f f u s u a l l y went t o the C a t h o l i c Church a b l o c k away where the masses were f r e q u e n t and q u i t e short. In 1950 we f l e w t o the Hague t o the Petroleum Congress — t h i s was h i s f i r s t f l i g h t a t age 82. As he s a i d , t h e r e was no p o i n t d o i n g something s m a l l , you might as w e l l f l y a c r o s s the A t l a n t i c . We boarded the p l a n e , s a t down, and a t t a k e o f f , the devout I p a t i e f f c r o s s e d h i m s e l f and l e f t i t i n God's hands. We d i d , however, r e t u r n on the Queen Mary. I t has been s a i d t h a t I was I p a t i e f f s protege and, f r a n k l y , knowing the man, I cannot t h i n k o f a g r e a t e r compliment. When he d e c i d e d t h a t I s h o u l d be on my own, he l e t go o f the r e i n s , but was always a v a i l a b l e f o r d i s c u s s i o n and c o n s u l t a t i o n , and anyone would have been v e r y f o o l i s h not t o take advantage o f that opportunity. The next attempt a t c a t a l y t i c r e f o r m i n g came a number o f y e a r s l a t e r . We had done some work on demethylation, then drifted into hydrocracking of kerosenes. That r e q u i r e d d e s u l f u r i z a t i o n and we were d e l i g h t e d a t how n e a t l y kerosenes c o u l d be hydroc r a c k e d over c a t a l y s t s l i k e n i c k e l - s i l i c a - a l u m i n a a t q u i t e low temperatures as l o n g as the s t o c k s were w e l l d e s u l f u r i z e d . One o f our t e s t s f o r six-membered r i n g naphthene c o n t e n t o f the g a s o l i n e p r o d u c t was the passage over p l a t i n u m on carbon at v e r y low space v e l o c i t i e s , wherein o n l y these p a r t i c u l a r naphthenes c o u l d be c o n v e r t e d i n t o a r o m a t i c s . Then we removed the a r o m a t i c s by s u l f u r i c a c i d treatment and e s t a b l i s h e d the f i v e carbon r i n g naphthene c o n t e n t o f spec i f i c f r a c t i o n s by a r e f r a c t i v e index measurement. Then came the i d e a t o t r e a t an e n t i r e g a s o l i n e f r a c t i o n , w e l l d e s u l f u r i z e d , over a p l a t i n u m c a t a lyst. V a r i o u s supports were made up and, as expected, we d i d c o n v e r t a p a r t o f the naphthenes i n t o a r o m a t i c s , but the octane number i n c r e a s e was n o t h i n g sensational. When we moved up i n temperature, the c a t a l y s t l a y down and d i e d . So we ran w i t h hydrogen and a p p l i e d a moderate p r e s s u r e . The r e s u l t s were not p a r t i c u l a r l y s t a r t l i n g but a t l e a s t the c a t a l y s t s u r v i v e d t h i s o r d e a l . So we kept moving up and, sure enough, we d i d get b e t t e r c o n v e r s i o n s . A l l t h i s time, we were j u s t b a r e l y keeping ahead w i t h our d e s u l f u r i z a t i o n runs t o make enough charge



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s t o c k f o r our d e h y d r o g e n a t i o n runs. One day we ran out o f d e s u l f u r i z e d s t o c k and used a v i r g i n s t r a i g h t run g a s o l i n e as our f e e d s t o c k . S u r p r i s i n g l y enough, the c a t a l y s t d i d not even bat an eye, but kept r i g h t on c o n v e r t i n g . By t h i s time we were a t about 450°C and 500 p s i g pressure and u s i n g about 5 moles o f hydrogen per mole o f f e e d . T h i s temperature was some 200 ° C higher than a t t h a t time recommended f o r a platinum c a t a l y s t . In r e t r o s p e c t , we had wasted a l o t o f time c l e a n i n g up the feed, but somehow the i d e a o f s u l f u r p o i s o n i n g was so i n g r a i n e d i n our minds t h a t the mere i d e a o f u s i n g a p o i s o n c o n t a i n i n g s t o c k was u n t h i n k able. A few o t h e r t h i n g s happened; we d i d n o t i c e t h a t now we were c o n v e r t i n g more naphthenes and t h a t some c r a c k i n g appeared t o take p l a c e . The c r a c k i n g helped to concentrate the a r o m a t i c s i n the p r o d u c t and thus enhanced the octane number. By t h i s time we were d o i n g about as w e l l as had been done p r e v i o u s l y w i t h a molybdenum o x i d e alumina c a t a l y s t , but w i t h c o n s i d e r a b l y l e s s carbon formation. So now t h i n g s became more s e r i o u s , but not s e r i o u s enough t o get p e o p l e v e r y e x c i t e d about i t . A f t e r a l l , we had been u s i n g a 3% p l a t i n u m on s i l i c a c a t a l y s t , and even i n those days 3% p l a t i n u m was p r e t t y expensive. P l a t i n u m on s i l i c a - a l u m i n a d i d much b e t t e r w i t h r e s p e c t t o octane number but we c o u l d not c o n t r o l the h y d r o c r a c k i n g v e r y w e l l , so we s w i t c h e d t o alumina which had an i n t e r m e d i a t e a c t i v i ty. The r e s u l t s looked p r e t t y good, p a r t i c u l a r l y because we c o u l d run f o r days w i t h o u t much l o s s i n activity. At t h i s p o i n t , I was quite fortunate i n that L a r r y G e r h o l d , who was a t t h a t time manager o f the l a b o r a t o r i e s , took q u i t e an i n t e r e s t i n the p r o j e c t and p o i n t e d out t o me a few f a c t s o f l i f e , one o f them b e i n g t h a t i f I were r e a l l y s e r i o u s about t h i s I b e t t e r s t a r t c u t t i n g down on the p l a t i n u m inventory on the c a t a l y s t . T h i s we d i d . I t i s s u r p r i s i n g what you can do when you have t o . We d e v i s e d a l l s o r t s o f schemes f o r i n c o r p o r a t i n g the p l a t i n u m i n t o the alumi n a , but one o b s e r v a t i o n was q u i t e c r i t i c a l , and t h a t was t h a t when we made the alumina from aluminum n i t r a t e i t was not so good a c a t a l y s t as one made from aluminum c h l o r i d e . T h i s was a real puzzle, u n t i l we o b s e r v e d t h a t l e s s washing o f the cake made from aluminum c h l o r i d e made a s t i l l b e t t e r c a t a l y s t . Then we found a s l i g h t a c i d i t y i n the e x i t gas from the u n i t and the p i c t u r e began t o g e l . If chlorine i s l o s t , but i s a c t i v e , then f l u o r i n e c o u l d be more



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a c t i v e and more s t a b l e . The f i r s t f l u o r i d e d c a t a l y s t gave us one o f the h i g h e s t octane p r o d u c t s we had ever o b t a i n e d . Thus, t h i n g s r e a l l y began t o look up. You can t e l l t h a t you have something good and t h i s , a t the time, l o o k e d extremely good. T h i s c a t a l y s t not o n l y gave a h i g h octane number p r o d u c t , i t a l s o had durab i l i t y , a t l e a s t i n the r e l a t i v e l y s h o r t t e s t s t h a t we were a b l e t o c a r r y out. W i t h i n a y e a r we had about one hundred p e o p l e working on the p r o j e c t -- a l a r g e p i l o t p l a n t crew, an e n g i n e e r i n g s t a f f and a substantial research effort, p r i m a r i l y devoted t o c a t a l y s t manufacture. I t would be o n l y f a i r t o name a l l the p e o p l e who c o n t r i b u t e d t o the p r o j e c t , but two p e r s o n s gave i t the g r e a t e s t push — they were L a r r y G e r h o l d and Bob Sutherland. I t has been o f t e n s a i d t h a t the most d i f f i c u l t s a l e i s w i t h i n your own company. Platformi n g s u f f e r e d the same f a t e and i t was l a r g e l y as a r e s u l t o f t h e e f f o r t s o f t h e s e i n d i v i d u a l s t h a t the p r o j e c t was not abandoned. One o f our t r o u b l e s was d e a c t i v a t i o n , i n f a c t , the p i l o t p l a n t o p e r a t i o n d i d show t h a t we d i d accumu l a t e carbon on the c a t a l y s t . I f the i n i t i a l r a t e o f carbon f o r m a t i o n were m a i n t a i n e d , the run would not l a s t more than a month or so. T h i s would mean regene r a t i o n , and i n s t e a d o f a r e l a t i v e l y simple o p e r a t i o n , we would have t o go t o a more complex p l a n t i n v o l v i n g a c y c l i c r e g e n e r a t i o n system and a l l i t s d i f f i c u l t i e s t h a t , a t t h a t time, were most f o r m i d able. F o r t u n a t e l y , as we l e a r n e d , the carbon format i o n d i d not c o n t i n u e but l e v e l e d out a t an a c c e p t able value. N e v e r t h e l e s s , our t r o u b l e s mounted. The c a t a l y s t requirement was a v e r y pure alumina s u b s t r a t e and t h a t meant t h a t we c o u l d not use a c o m m e r c i a l l y supp l i e d m a t e r i a l which c o n t a i n e d i r o n and o t h e r i m p u r i t i e s which s e r i o u s l y i m p a i r e d the a c t i v i t y . The i n i t i a l l a r g e r s c a l e c a t a l y s t manufacture was done by p u r i f y i n g anhydrous aluminum c h l o r i d e by r e d i s t i l l a t i o n and then h y d r o l y z i n g i t , f o l l o w e d by f i l t r a t i o n , washing, d r y i n g , p i l l i n g , impregnation, e t c . F u r t h e r more, m i s g i v i n g s began t o a r i s e . We were c o n s i d e r i n g a c a t a l y s t which would c o s t about $10.00 per pound, compared t o the u s u a l c a t a l y s t c o s t o f about 15-60 c e n t s a pound. The s a l e s department was not too fond o f the new p r o c e s s — i t was too r a d i c a l a d e p a r t u r e from the p r o c e s s e s they were used t o s e l l i n g . The s e r v i c e department, which o v e r s e e s the commercial o p e r a t i o n s , was a l s o r a t h e r lukewarm about the whole



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b u s i n e s s , and advocated more p i l o t p l a n t t e s t i n g and some m o d i f i c a t i o n s . At t h i s d a r k e s t hour, the p r o j e c t was r e s c u e d by Mr. D a v i d H a r r i s , p/^esident o f UOP. He decided..to go ahead. I t i s amazing how many p e o p l e f a l l i n l i n e when the boss makes a d e c i s i o n ! I t must have been a d i f f i c u l t d e c i s i o n . Mr. H a r r i s took over the management o f UOP i n 1945 a f t e r i t was g i v e n t o the ACS by the former owners, the major o i l companies. Very l i t t l e cash was a v a i l a b l e and, a t the time o f the g i f t , the cupboard was p r e t t y bare. Even more d i s t u r b i n g was t h a t the b a s i c p a t e n t s i n t h e r m a l c r a c k i n g were e x p i r i n g , c u t t i n g o f f a d d i t i o n a l revenue, and, f u r t h e r m o r e , the company was a l s o f a c i n g some 60 m i l l i o n d o l l a r s worth o f l e g a l suits against i t . To Mr. H a r r i s , a v e r y s u c c e s s f u l businessman, t h i s was q u i t e a c h a l l e n g e . H i s number one job was to o r g a n i z e the company o p e r a t i o n on a more b u s i n e s s l i k e b a s i s and then s e t t l e the l e g a l s u i t s . As he said: " o n l y the lawyers get r i c h " , and c a r r i e d t h i s message i n h i s v i s i t s t o the o p p o s i n g p a r t i e s i n the s u i t s , and d i d h i s v e r y b e s t i n s t a v i n g o f f p o s s i b l e bankruptcy. ( A c t u a l l y , Mr. H a r r i s , i n h i s remark about the lawyers, d i d not f o r e s e e the dilemma o f a lawyer who had t o c a l l a plumber t o unplug a s i n k . A f t e r the work was done i n about 3/4 o f an hour, the lawyer was p r e s e n t e d w i t h a b i l l f o r 75 d o l l a r s . The lawyer e x c l a i m e d : "You know, t h i s amounts t o 100 d o l l a r s an hour, and even I, as a lawyer, do not make t h a t much per hour", t o which the plumber r e p l i e d : "I d i d not e i t h e r , when I was a lawyer.") When i t came t o r e s e a r c h and development, Mr. H a r r i s knew i t was the one s u b s t a n t i a l a s s e t he must keep i n t a c t and make p r o f i t a b l e . To him, P l a t f o r m i n g r e p r e s e n t e d a s u b s t a n t i a l investment but the p o t e n t i a l was g r e a t and he t r u s t e d h i s a d v i s o r s . His gamble d i d pay o f f and w i t h i n t e n y e a r s UOP, a l r e a d y f r e e o f l e g a l s u i t s , was s o l d t o the p u b l i c f o r about 75 m i l l i o n d o l l a r s , chus p r o v i d i n g a r e a l bonanza f o r the Petroleum Research Fund a d m i n i s t e r e d by the ACS. Although P l a t f o r m i n g was a very substantial c o n t r i b u t o r t o the w e l f a r e o f the company, the o v e r a l l e f f o r t s i n o t h e r a r e a s , such as c a t a l y t i c c r a c k -



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ing, a l k y l a t i o n and o t h e r r e f i n i n g p r o c e s s e s , also p i c k e d up and r e s u l t e d i n c o n s i d e r a b l e income. D u r i n g the first t e n years a f t e r the process was first announced, P l a t f o r m i n g u n i t s were l i c e n s e d a t t h e average r a t e o f one every two weeks, so t h a t by 1960 some 230 u n i t s were i n o p e r a t i o n , representing a c a p a c i t y o f some 1.5 m i l l i o n b a r r e l s p e r day. At t h e p r e s e n t time, t h e t o t a l l i c e n s e e P l a t f o r m i n g c a p a c i t y i s i n excess o f 4 m i l l i o n b a r r e l s p e r day w i t h n e a r l y 500 u n i t s i n o p e r a t i o n . We have c a t a l y s t manufacturing facilities i n the United States, Europe and Japan. N e e d l e s s t o say, anytime something l i k e this comes a l o n g you g e t a f a i r number o f c o m p e t i t o r s , so t h a t t h e t o t a l volume o f g a s o l i n e produced i n p l a t i num containing catalytic reforming u n i t s i s very large. In f a c t , a t t h e p r e s e n t time one would be h a r d p r e s s e d t o buy g a s o l i n e which d i d n o t c o n t a i n a p o r t i o n p r o c e s s e d over a p l a t i n u m c a t a l y s t . You might wonder how t h e name " P l a t f o r m i n g " was coined. In r e t r o s p e c t , p l a t i n u m r e f o r m i n g shortened to P l a t f o r m i n g was a c l e v e r c o n d e n s a t i o n and was thought up by Horner Eby, one o f the t h r e e c h e m i s t s t h a t comprised our group a t t h a t time. I t was c l e v e r because i t was d e s c r i p t i v e and a l s o i m p l i e d e l e v a t i o n , and we d i d mean e l e v a t i o n i n octane number and yield. Our p u b l i c r e l a t i o n s department, whose domain was t o t h i n k up names, took a dim view o f t h e name we used and thought up a number o f a l t e r n a t i v e s , b u t , l i k e most f o r c e d - t o - t h i n k - u p - i d e a s , they f a r e d p o o r l y and t h e name had s t u c k f o r l a c k o f b e t t e r ones. The name " P l a t f o r m a t e " i m p l i e d t h e p r o d u c t from the P l a t f o r m i n g p r o c e s s and we used i t e x t e n s i v e l y . The S h e l l Company asked us f o r t h e r i g h t s t o use i t i n t h e i r a d v e r t i s i n g campaign. The g r e a t e r m i l e a g e due t o t h e use o f P l a t f o r m a t e was q u i t e r e a l and a r o s e from t h e f a c t t h a t when you have more a r o m a t i c s present t h e g a s o l i n e i s more dense and, on a p e r g a l l o n b a s i s , more t o t a l BTU s a r e produced on combustion . None o f t h i s d i d we f o r e s e e i n t h e s p r i n g o f 1949. The f i r s t p u b l i c announcement o f t h e new p r o c e s s was v e r y i n a u s p i c i o u s . The " s o f t s e l l " was d e c i d e d upon, p r o b a b l y from n e c e s s i t y , because we 1

American Chemical Society Library 1155 16th St. N. W. 0. C. 20038 DavisWashington, and Hettinger; Heterogeneous Catalysis ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

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c o u l d h a r d l y a f f o r d an a l l - o u t s a l e s campaign. Ed Nelson, a v i c e - p r e s i d e n t o f UOP and a g r e a t s u p p o r t e r o f the p r o c e s s , had been asked t o d e l i v e r a g e n e r a l paper on r e c e n t t r e n d s i n p e t r o l e u m t e c h n o l o g y a t the Western Petroleum R e f i n e r s ' A s s o c i a t i o n Meeting i n A p r i l o f 1949 i n San A n t o n i o . In t h i s paper, as one o f f i v e items, he i n c l u d e d s e v e r a l paragraphs genera l l y describing Platforming. But t h i s proved t o be enough. The s u p e r i n t e n d ent o f the O l d Dutch R e f i n e r y a t Muskegon, Michigan, Elmer Sondregger, heard the paper and stopped a t UOP ' s o f f i c e s on the way home from the meeting t o p l e a d t h a t we i n s t a l l the f i r s t u n i t o f the new p r o cess at h i s r e f i n e r y . He had a t h e r m a l r e f o r m i n g u n i t which he would make a v a i l a b l e f o r revamping t o Platforming. The o f f e r was accepted, and the next s i x months were busy ones around UOP. A l l records were broken i n c a r r y i n g out the d e s i g n , purchasing and c o n s t r u c t i o n i n t h i s s h o r t p e r i o d . Many l a b o r a t o r y and p i l o t p l a n t runs had t o be made t o p r o v i d e s p e c i f i c answers t o problems which a r o s e . Probably the most c r i t i c a l item was the manufacture o f commerc i a l q u a n t i t i e s o f a c a t a l y s t which had p r e v i o u s l y been made o n l y i n s m a l l l a b o r a t o r y b a t c h e s . By November, the c o n s t r u c t i o n was completed, c a t a l y s t s u p p l i e d and the u n i t was ready t o s t a r t . I was d e l i g h t e d t o be asked t o a t t e n d the s t a r t - u p t h a t f a t e f u l Saturday a f t e r n o o n . I had been w i t h the company some 12 y e a r s and d u r i n g t h a t time, except f o r a few s c i e n t i f i c accomplishments and a number o f p a t e n t s , I had not r e a l l y c o n t r i b u t e d t o the company's w e l f a r e . So t h i s was the f i r s t o p p o r t u n i t y t o j u s t i f y some o f the investment the company had i n me. The u n i t s t a r t e d up b e a u t i f u l l y , but d i s a s t e r — at l e a s t i t seemed l i k e a d i s a s t e r -- s t r u c k i n about t h r e e hours on stream, and the u n i t had t o be shut down. What do you do when a d i s a s t e r , such as t h i s o b v i o u s l y was, r e a l l y s t r i k e s ? You r e t i r e t o a bar. There was o n l y one t o p i c o f c o n v e r s a t i o n . In the m i d d l e o f i t , Howard Nebeck, a most c a p a b l e chemical engineer, l e f t without f i n i s h i n g h i s d r i n k and r e t i r e d t o h i s room t o do some s k e t c h e s on the r e d e s i g n o f the r e a c t o r . The problem was excessive overheating o f the outer s h e l l . I s t i l l remember the f r e q u e n c y with which George Thompson, the UOP o p e r a t o r i n charge o f the u n i t , was a p p l y i n g the temperature c h a l k s t o the outer shell. When the h i g h e s t temperature chalk promptly m e l t e d on the s h e l l , he p u l l e d the s w i t c h



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and t h e u n i t went down. I should e x p l a i n that the c a t a l y s t was c o n t a i n e d i n an i n s i d e i n s u l a t e d r e a c t o r , and t h e h i g h temperature i n s u l a t i o n was supposed t o p r o t e c t t h e carbon s t e e l s h e l l from t h e combined e f f e c t s o f h i g h temperature and h i g h hydrogen p a r t i a l pressure. A p p a r e n t l y t h e i n s u l a t i o n was n o t i n s u l s ting properly. Howard Nebeck's r e d e s i g n t h a t n i g h t i n v o l v e d a new l i n e r c o n f i g u r a t i o n and, seven days l a t e r , t h e u n i t was m o d i f i e d and brought back on stream, t h i s time t o r u n f o r about n i n e months on t h e same b a t c h o f c a t a l y s t . The p r o c e s s proved t o be e x a c t l y t h e r i g h t s o l u t i o n t o O l d Dutch's problems. Where p r e v i o u s l y t h e g a s o l i n e from t h e r e f i n e r y had been p i l i n g up i n i t s tanks w i t h no customers, everyone seemed anxious t o try new " p l a t i n u m t r e a t e d " g a s o l i n e . T h i s market r e q u i r e d a d d i t i o n a l f e e d s t o c k s and i n o r d e r t o meet this sudden need, the area around Muskegon was s c o u r e d f o r a l l a v a i l a b l e naphthas. Among t h e s t o c k s f e d t o t h e u n i t was a v e r y h i g h s u l f u r bottoms p r o d uct from l i g h t g a s o l i n e sweetening r e r u n n i n g , and a used c h l o r i n a t e d c l e a n i n g s o l v e n t . Some o f t h e s e s t o c k s d i d n ' t r u n v e r y w e l l , b u t t h e u n i t d i d manage to s u r v i v e and some o f t h e l i m i t a t i o n s o f t h e p r o c e s s were q u i c k l y d e f i n e d . From t h e s t a r t , t h e r e was q u i t e a stream o f v i s i t o r s t o see t h e u n i t i n o p e r a t i o n . We even had a sample o f " c a t a l y s t " i n a g a l l o n c o n t a i n e r as an e x h i b i t i n the o f f i c e o f the p l a n t . The volume o f the sample shrank i n p r o p o r t i o n t o t h e number o f v i s i t o r s , who undoubtedly j u s t wanted a s o u v e n i r . I would have h a t e d t o have them be m i s l e d by an a n a l y s i s of that p a r t i c u l a r souvenir. D e s p i t e e x t e n s i v e p u b l i c i t y and a good performance, we d i d n o t s t a r t up t h e second u n i t f o r about two y e a r s . In a way, t h i s c o u l d have been a good thing. I t gave us a chance t o c o n s o l i d a t e our p o s i t i o n by l e a r n i n g a g r e a t d e a l more about t h e p r o c e s s and, a t t h e same time, make some s u b s t a n t i a l improvements. In a d d i t i o n , t h e c o m p e t i t i o n was l u l l e d i n t o a f a l s e f e e l i n g o f s e c u r i t y and we g a i n e d t h e most important element — time. The c h i e f c o m p e t i t o r was f l u i d h y d r o f o r m i n g and c o n s i d e r a b l e improvements were b e i n g made i n t h e p r o c e s s . I remember w e l l a v e r b a l b a t t l e a t t h e World Petroleum Congress a t The Hague between t h e proponents o f f l u i d hydroforming and ourselves. We had a good t h i n g and we knew i t , but t h e y f e l t t h e same way and by sheer mass they c o u l d and d i d swing a l o t o f weight. The next y e a r s e t t l e d the i s s u e , and s a l e s o f P l a t f o r m i n g u n i t s i n c r e a s e d



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very r a p i d l y . Here a g a i n , we were f o r t u n a t e i n g e t t i n g some o f the majors i n t e r e s t e d enough t o s i g n up, and once you do t h a t i t i s j u s t l i k e g e t t i n g support from Mayor Daley. You graduate i n t o the b i g time. Here a g a i n , I must emphasize t h a t throughout the whole time the r a t r a c e c o n t i n u e d , p r i m a r i l y due t o the p r e s s u r e s e x e r t e d from w i t h i n the company, from people l i k e Gerhold, who weren't s a t i s f i e d w i t h the s t a t u s quo. Our c a t a l y s t m a n u f a c t u r i n g method was r a t h e r complex and c o s t l y . The new method, developed from the v e r y i n g e n i o u s work by Jim Hoekstra, made a l l the d i f f e r e n c e i n the w o r l d by p r o v i d i n g f o r a much b e t t e r c a t a l y s t support, made by a c o n t i n u o u s p r o c e s s o f manufacture. But even t h i s proved t o be a d i f f i c u l t t h i n g t o put on the marketplace, s i n c e r e f i n e r s who had the o l d c a t a l y s t i n t h e i r u n i t s , d i d not r e a l l y want t o change, so we had t o m a i n t a i n d u p l i c a t e f a c i l i t i e s f o r a p e r i o d o f time. The p e r formance i n the f i e l d was good enough t o a t t r a c t i m i t a t i n g competitors. One d i s t u r b i n g o c c u r r e n c e r e a l l y shook us. A P l a t f o r m i n g u n i t a t B e l l O i l and Gas Company was s t a r t e d and r a n v e r y w e l l f o r a few weeks — then r e p o r t s s t a r t e d coming i n t h a t a l l was not w e l l . T h i s i s t y p i c a l , you are slow t o hear o f the good performance, but the poor ones r e a c h you q u i c k l y . The a i l m e n t was q u i t e r e a l . The temperature drop a c r o s s the f i r s t r e a c t o r d e c l i n e d from the normal 100° F t o about 30° F and the second r e a c t o r took over the r e a c t i o n . However, t h i s a l s o s t a r t e d t o l o s e a c t i v i t y and the h e a t e r s c o u l d not keep up w i t h the demand f o r a d d i t i o n a l heat t o m a i n t a i n the o v e r a l l activity. F i n a l l y the u n i t was shut down and the c a t a l y s t from the f i r s t o f the t h r e e r e a c t o r s was r e t u r n e d t o us f o r examination. Here a g a i n , we were f o r t u n a t e i n h a v i n g a s t u t e people on our s t a f f , l i k e Jack Murray and Ed B i c e k o f our P h y s i c a l and A n a l y t i c a l Research. T h i s group developed new analytical p r o c e d u r e s which i d e n t i f i e d a r s e n i c as the p o i s o n i n g f a c t o r , and t r a c e d i t t o the f e e d s t o c k . The a r s e n i c was p r e s e n t t o the e x t e n t o f o n l y about 30 p a r t s per billion. The p l a t i n u m i n the c a t a l y s t j u s t l o v e d the a r s e n i c , even i n these low c o n c e n t r a t i o n s , and we were showing good p a t t e r n s o f p l a t i n u m arsenide. I f the u n i t i n the f i e l d showed d e a c t i v a t i o n , we s h o u l d be a b l e t o do so i n the l a b o r a t o r y , so we added a few p a r t s per m i l l i o n o f an o i l s o l u b l e a r s e n i c compound t o a c l e a n f e e d and, d e s p i t e a f a i r l y long run, c o u l d not show any poisoning effect. F i n a l l y , we r e a l i z e d t h a t i n a l a b o r a t o r y u n i t the



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s u r f a c e t o volume r a t i o o f the hardware was many orders o f magnitude g r e a t e r than i n a commercial u n i t , and we were undoubtedly p i c k i n g up the i m p u r i t y s e l e c t i v e l y on the w a l l s o f the hardware p r i o r t o e n t r y i n t o the c a t a l y s t bed. As a l a s t r e s o r t , we suspended a minute p a r t i c l e o f a r s e n i c i n the gas phase o f the p r e h e a t e r and, sure enough, we d e a c t i v a ted the c a t a l y s t w i t h i n hours. The s t o r y o f the a r s e n i c p o i s o n i n g t r o u b l e s d i d reach the i n d u s t r y b e f o r e we had demonstrated a s o l u t i o n t o the problem, and some o f our newly e s t a b l i s h e d competitors were p u b l i c i z i n g t h e i r platinum c a t a l y s t as p o i s o n r e s i s t a n t . T h i s c r e a t e d a minor u p r o a r w i t h i n UOP, and some o f the p e o p l e who got on the P l a t f o r m i n g bandwagon by e d i c t were a g a i n v o i c i n g their misgivings. Before too l o n g the whole t h i n g d i e d down, i n c l u d i n g the c l a i m s o f the c o m p e t i t o r s . I s u s p e c t t h a t they had f a l l e n i n t o the same t r a p t h a t we had by r e l y i n g upon a l a b o r a t o r y t e s t . D e s p i t e a l l t h i s the p o i s o n i n g was r e a l — and the o n l y way out was a pretreatment o f the f e e d and t h i s was r e a d i l y accomplished by a t r e a t i n g s t e p p r i o r t o f e e d i n g the s t o c k t o the P l a t f o r m e r . Thus, we became q u i t e aware o f the e f f e c t o f p o s s i b l e p o i sons, and as the octane number r e q u i r e m e n t s became more severe we l e a r n e d t o i n s t a l l more s o p h i s t i c a t e d pretreating facilities. P l a t i n u m i s a s c a r c e m a t e r i a l , and the success o f the p r o c e s s depended on development o f an economical p r o c e s s f o r r e c o v e r i n g i t from spent c a t a l y s t . T h i s was v e r y w e l l handled by Herb A p p e l . On the o t h e r hand, c a t a l y s t m o d i f i c a t i o n s have proven t o be a c o n t i n u i n g problem. In r e t r o s p e c t , i t i s amazing how one does not l e a r n from h i s t o r y . When U n i v e r s a l was d e e p l y i n v o l v e d i n s y n t h e t i c c r a c k i n g c a t a l y s t s , new catalyst m o d i f i c a t i o n s were always t e s t e d a t the same c o n d i t i o n s t h a t were developed f o r the i n i t i a l c a t a l y s t s , and i t i s no wonder the new c a t a l y s t s d i d not s t a n d much o f a chance. We f e l l i n the same t r a p w i t h the m o d i f i e d c a t a l y s t s i n the P l a t f o r m i n g s e r i e s and a number o f good compositions were o v e r l o o k e d for a time because they were t e s t e d a t tfre c o n d i t i o n s found best f o r the reference catalysts. Nevertheless, advances were made and, from the i n i t i a l R-4 catal y s t , , as i t was c a l l e d , we have gone through a s u b s t a n t i a l number o f commercial c a t a l y s t s so t h a t now we are i n the R-30 s e r i e s w i t h the most s o p h i s t i cated bimetallic catalysts, the new developments coming l a r g e l y through the e f f o r t s o f E r n i e P o l l i t z e r and John Hayes and t h e i r group.




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Throughout a l l t h i s work, one f a c t has emerged most c l e a r l y . You can t h i n k up a l l s o r t s o f c a t a l y s t c o m p o s i t i o n s , but they are o f no a v a i l u n l e s s t h e y are p r o p e r l y tested. The proper t e s t i n g implies m e t i c u l o u s a t t e n t i o n t o the d e s i g n and d e t a i l s o f the t e s t and p r o p e r i n t e r p r e t a t i o n o f the r e s u l t s . I t i s p e o p l e l i k e Rod Donaldson and a number o f o t h e r most c a p a b l e c h e m i c a l e n g i n e e r s who have made t h i s worx m e a n i n g f u l and u s e f u l f o r f u r t h e r c a t a l y s t d e v e l o p ment . At the same time, the s e a r c h c o n t i n u e s f o r the u n d e r s t a n d i n g o f how t h e s e c a t a l y s t s can be c h a r a c t e r i z e d by means o t h e r than the c a t a l y t i c a c t . We are now f i n d i n g t h a t such c h a r a c t e r i z a t i o n appears t o be a r e a l i t y , i n o t h e r words, through the work done by the group headed by Hertha S k a l a , we have d e v e l oped new i n s i g h t o f the r e l a t i o n s h i p between the m e t a l l i c components and the s u b s t r a t e . At t h i s p o i n t , I would l i k e t o d i g r e s s t o ment i o n an important segment o f the r e s e a r c h e f f o r t . In the development o f the R s e r i e s o f c a t a l y s t s , we have been v e r y f o r t u n a t e i n h a v i n g on our s t a f f a number o f t e c h n i c i a n s who, d e s p i t e the l a c k o f formal t e c h n i c a l degree, were a b l e t o c o n t r i b u t e s u b s t a n t i a l l y t o the development o f new catalysts. In f a c t , a number o f our commercial c a t a l y s t s do bear the d i s t i n c t mark o f c o n t r i b u t i o n by t h e s e p e o p l e . We l i k e t o t h i n k t h a t our method o f o p e r a t i o n , which i n c l u d e s t h e i r p a r t i c i p a t i o n i n our d i s c u s s i o n s e s s i o n s and p r o v i d i n g f o r them an o p p o r t u n i t y t o t r y out t h e i r own i d e a s , has a d i r e c t b e a r i n g on t h e i r growth. We, i n t u r n , b e n e f i t and we r e c o g n i z e t h e i r c o n t r i b u t i o n s by t a k i n g them o f f h o u r l y pay and p u t t i n g them on a s a l a r y b a s i s , commensurate w i t h p r o f e s s i o n a l s t a t u s . Thus, i t i s q u i t e apparent t h a t any t e c h n i c a l development i s o n l y as good as the i n t e r e s t you can arouse i n p e o p l e . There are those you work f o r , t h o s e w i t h whom you work, and t h o s e who work f o r you. The more u n u s u a l the i d e a the more d i f f i c u l t i s the s a l e , but the p e o p l e who get s o l d on the unusual i d e a are the r e a l t o p - n o t c h e r s , and once t h e s e c r i t i c a l p e o p l e are s o l d , the i n p u t on t h e i r p a r t i s tremend o u s l y important f o r the f i n a l t e c h n o l o g i c a l s u c c e s s . In r e t r o s p e c t , I can o n l y say t h a t i t was, and s t i l l i s , a wonderful e x p e r i e n c e . To me one o f the greatest t h r i l l s i s t o see a l a r g e s c a l e u n i t i n o p e r a t i o n which i s based i n p a r t on your own e f f o r t s . This t h r i l l i s g r e a t e r than a l l the advancements, f i n a n c i a l g a i n s and honors t h a t may come your way. RECEIVED December 1,

1982


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