Heterogeneous Catalysis - ACS Publications - American Chemical

3 V. Ν. Ipatieff: As I Knew Him

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H E R M A N PINES Northwestern University, The Ipatieff Catalytic Laboratory, Department of Chemistry, Evanston, IL 60201

In the late 1920s, the industrialized nations were greatly concerned about a shortage of petroleum--the rich Texas oil pools and the vast Arabian deposits were unknown. There was therefore much interest in the possible catalytic conversion of coal to motor fuel, and Universal Oil Products Company, then licensor of thermal-cracking processes to the oil industry, had decided to build a research competence in catalysis. The director of research for UOP, Dr. Gustav Egloff, was commissioned to search everywhere for catalytic experts. Egloff met Ipatieff in Germany and invited him to visit Chicago. Ipatieff arrived for exploratory talks in 1930, and was asked to organize a research laboratory at Universal Oil Products for studying the catalytic conversions of petroleum hydrocarbons. He accepted the offer and returned to Germany to f u l f i l l an industrial consulting commitment and to await a permanent visa to enter the U.S. It was not easy for a Russian citizen to obtain such a visa at that time, and Ipatieff eventually came to the U.S. through the efforts of Ward V. Evans, Chairman of the Department of Chemistry at Northwestern. Ipatieff s academic visa permitted him and his wife to establish their permanent residence here. Eight years later, in appreciation of Northwestern's friend ship and assistance, Ipatieff donated funds for the establishment of the Ipatieff High-Pressure and Catalytic Laboratory at the university, and eventually willed his estate to i t . In the few years between 1930 when Ipatieff first arrrived in the United States, commencing a new career at a time when most men retire, and his 70th birthday party in 1937, arranged by the Chicago Section of ACS, he had published many research papers, was granted 14 U.S. patents, applied for 50 more, written a book, his chemical autobiography, and discovered processes for produ cing high octane aviation gasoline. My association with Ipatieff dates from the day of his arrival in this Country and over the years we became close f

0097-6156/83/0222-0023$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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HETEROGENEOUS CATALYSIS

f r i e n d s . I p a t i e f f was one of chemistry's great pioneers. His productive work spanned 60 years, from h i s f i r s t research paper i n 1892 u n t i l h i s death i n 1952 at the age of 85. T h i s was an extraordinary accomplishment f o r anyone—an almost unimaginable feat f o r a man t r a i n e d i n h i s youth f o r the Russian army, and f o r one whose l i f e was d i r e c t l y a f f e c t e d by the F i r s t World War, the Russian Revolution, the S t a l i n i s t p o l i c e s t a t e , and emigration. V l a d i m i r N i c o l a e v i t c h I p a t i e f f was born i n t o the minor Russian n o b i l i t y i n Moscow on Nov. 21, 1867. His f a t h e r was an architect. At h i s f a t h e r ' s wish, I p a t i e f f entered a m i l i t a r y school, where he began as a mediocre student. When he was about 14, h i s i n t e r e s t was quickened by s c i e n c e , e s p e c i a l l y mathematics and chemistry. He continued h i s education at the M i k h a i l A r t i l l e r y School i n St. Petersburg, where the main f i e l d s were mathematics and b a l l i s t i c s . The chemistry curriculum was so i n e f f e c t i v e that I p a t i e f f began a program of s e l f - s t u d y . The few Russian chemi s t r y texts became h i s teachers; he read and reread them and c a r r i e d out the experiments they d e s c r i b e d . In 1887, when he graduated with highest grades as an o f f i c e r i n the Tsar's army, he r e c e i v e d money from the government and from h i s f a t h e r to purchase a uniform, a saddle, and other equipment. He used part of the money to put together a small l a b o r a t o r y . And so, with l i m i t e d f a c i l i t i e s , he acquired a fundamental knowledge of i n o r g a n i c chemistry at h i s l e i s u r e . A f t e r two years as a f i e l d o f f i c e r , I p a t i e f f entered the A r t i l l e r y Academy i n St. Petersburg. The academy o f f e r e d advanced t e c h n i c a l t r a i n i n g to o f f i c e r s , but i t s chemistry laboratory was i l l - e q u i p p e d . I p a t i e f f requested permission from the a u t h o r i t i e s to b u i l d a small l a b o r a t o r y i n h i s apartment. Permission was needed because i n those days of p o l i t i c a l u n r e s t , home l a b o r a t o r i e s sometimes produced bombs. In t h i s l a b o r a t o r y he i n v e s t i g a t e d the s t e e l used i n making guns, and i n 1892 published the f i r s t of s e v e r a l hundred research papers. In the same year, he was appointed i n s t r u c t o r i n chemistry at the academy and he married Barbara Ermakova. I p a t i e f f r e a l i z e d that h i s knowledge of organic chemistry was inadeqaute, and he approached Professor A. E. Favorsky of St. Petersburg U n i v e r s i t y f o r advice. As a r e s u l t of Favorsky's recommendation, I p a t i e f f began to attend Menshutkin's l e c t u r e s i n organic chemistry and at the same time worked under Favorsky*s guidance on h i s d i s s e r t a t i o n e n t i t l e d , "The Isomerization of Alkenes and Acetylenes," f o r which he was awarded the B u t l e r o v P r i z e . He was promoted soon to the rank of A s s i s t a n t P r o f e s s o r at the Academy. In 1896 I p a t i e f f spent a year i n Germany i n the l a b o r a t o r y of the great Adolph von Baeyer. In the l a b o r a t o r y he made f r i e n d s with Moses Gomberg, the d i s c o v e r e r of s t a b l e f r e e r a d i c a l s ( U n i v e r s i t y of Michigan) and Richard W i l s t a t e r , l a t e r r e c i p i e n t of a Nobel P r i z e . The three of them met i n Chicago i n 1933

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

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V. Ν. Ipatieff: As 1 Knew Him

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during the ACS meeting (Figure 1). On r e t u r n i n g to St. P e t e r s burg, I p a t i e f f expanded h i s research s t a r t e d i n Germany and pre sented an advanced d i s s e r t a t i o n . In 1898 he became the A r t i l l e r y Academy's f i r s t P r o f e s s o r of Chemistry.

The entrance of I p a t i e f f i n t o c a t a l y t i c research occurred i n 1900. He n o t i c e d that when isoamyl a l c o h o l was passed through a heated i r o n tube, what emerged was not the a l c o h o l but the a l d e hyde and hydrogen and that when the a l c o h o l was passed through a heated quartz tube, i t emerged unchanged: CH

3

I p a t i e f f r e a l i z e d that he had encountered a new phenomenon, contact c a t a l y s i s . Thus began 50 years of f r u i t f u l work i n a new field. An avalanche of d i s c o v e r i e s f o l l o w e d — t h e dehydration of a l c o h o l s over alumina, c a t a l y t i c i s o m e r i z a t i o n of o l e f i n s , con v e r s i o n of ethanol to butadiene. Another major accomplishment was h i s i n t r o d u c t i o n i n 1905 of an autoclave to c o n t a i n r e a c t i o n s at high pressures and temperatures. H i s e a r l y t r a i n i n g as an a r t i l l e r y o f f i c e r enabled him to develop a t i g h t s e a l f o r the autoclave which could withstand high pressures never before a t t a i n e d , thus opening a new e r a i n the i n v e s t i g a t i o n of c a t a l y t i c reactions. Using h i s newly discovered high-pressure technique, I p a t i e f f studied hydrogénation of organic compounds i n the l i q u i d phase. The pressure technique enabled I p a t i e f f f o r the f i r s t time to achieve complete hydrogénation of benzene to cyclohexane and of phenol to cyclohexanol. I p a t i e f f used h i s pressure technique to the study of p o l y merization of o l e f i n s , hydrogénation of sugars, and displacement of metals (forerunner of hydrometallurgy). A l l t h i s he accomp l i s h e d with untrained a s s i s t a n t s s i n c e there were no students s p e c i a l i z i n g i n chemistry at the Academy of A r t i l l e r y . He was honored repeatedly f o r h i s s c i e n t i f i c accomplishments, and i n 1916 he became a member of the Russian Academy of Sciences and a commander of the French Legion of Honor. M i l i t a r y promotions accumulated. By 1910, he was a major general, by 1914, a l i e u t e n a n t general (Figure 2 ) . Although these ranks e n t i t l e d him to be addressed as "Your E x c e l l e n c y , " he i n s i s t e d that h i s l a b o r a t o r y colleagues r e f e r to him by h i s f i r s t name and patronymic. (Later, i n the U.S., he p r e f e r r e d to be c a l l e d " P r o f e s s o r " ) .



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Figure 1.

V. N. Ipatieff ( l e f t ) , R. Willstatter (center) and M. Gomberg at an ACS meeting i n Chicago, IL, 1933.

Figure 2.

Ipatieff as Lt. General of the Russian Army, 1916.


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V. Ν. Ipatieff: As I Knew Him

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World War I and R e v o l u t i o n On the outbreak of the F i r s t World War, Tsar Nicholas I I placed I p a t i e f f i n charge of the nationwide chemical i n d u s t r y to serve Russia's wartime needs and to prepare f o r the eventual r e t u r n to peace. In e f f e c t , I p a t i e f f presided over the b i r t h of the modern chemical i n d u s t r y i n h i s country. E a r l y i n 1917, the Russian government ceased f u n c t i o n i n g . One evening i n February, c r o s s i n g the f r o z e n Neva River on h i s way home from h i s army o f f i c e , I p a t i e f f encountered a mob of r i o t e r s . He l a t e r described the event: " I owe my l i f e to the lucky chance of meeting a s o l d i e r whom I knew ···· I t was o u t r i g h t s u i c i d e f o r a general to appear i n uniform before the angry mob, and at l e a s t 10 generals and many o f f i c e r s were k i l l e d that day. Without Romashev's help, I never would have reached home · " The f i r s t years of the Revolution were d i f f i c u l t . Lack of f a c i l i t i e s , food, and f u e l made f o r i n a c t i v i t y . Aware of I p a t i e f f ' s wartime c o n t r i b u t i o n to the development of the Russian chemical i n d u s t r y , Lenin made him a member of the Presidium of the Supreme C o u n c i l of the N a t i o n a l Economy and chairman of the chemical a d m i n i s t r a t i o n . I p a t i e f f thus became the only nonmember of the Communist Party i n the Soviet higher government. Although h i s governmental duties occupied much of I p a t i e f f ' s time, he s t i l l was able to continue h i s s c i e n t i f i c work and to study the d e s t r u c t i v e hydrogénation of hydrocarbons. On Lenin's death i n 1924, S t a l i n came to power. I p a t i e f f was removed from high o f f i c e , but he organized another l a b o r a t o r y . He devoted h i s time to research and during 1927 and 1928 I p a t i e f f published many more research papers, and the honors kept coming. Then, a c l o s e a s s o c i a t e and f r i e n d , Ε. I . S p i t a l s k y , was a r r e s t e d by the dreaded s t a t e p o l i c e i n 1929, and f i v e of h i s former students and co-workers had been shot without a t r i a l . A r r e s t s of many other a s s o c i a t e s followed. He was s e c r e t l y warned that he was to be a r r e s t e d . In June of that year he and h i s wife l e f t Russia f o r a s c i e n t i f i c meeting i n Germany. At the P o l i s h border he turned to her and s a i d , "Take a good look at your country, Barbara, as we are l e a v i n g i t f o r good." Emigration Once s e t t l e d , I p a t i e f f d i v i d e d h i s a c t i v i t i e s between U n i v e r s a l O i l P r o d u c t s and N o r t h w e s t e r n s C h e m i s t r y D e p a r t m e n t , where he spent two days a week t r a i n i n g g r a d u a t e s t u d e n t s , d i r e c t i n g r e s e a r c h , and c a r r y i n g on e x p e r i m e n t s w i t h h i s own hands ( F i g u r e 3 ) . These f i r s t months i n t h e new l a n d were g r u e l i n g . He was i n h i s s i x t i e s . He d i d n o t know E n g l i s h . H i s a s s i s t a n t s d i d n o t know R u s s i a n , German, o r F r e n c h . T h r o u g h s h e e r p e r s e v e r a n c e and l o n g h o u r s , h i s spoken E n g l i s h i m p r o v e d s t e a d i l y , t h o u g h he n e v e r became f l u e n t . When he was t o speak 1



Inlet


Gas

Figure 3-

Ipatieff Type Rotating Autoclave.


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p u b l i c l y , he wrote out h i s l e c t u r e s i n Russian, had them t r a n s l a t e d i n t o E n g l i s h , and spent hours reading them to h i s t u t o r .


At u n i v e r s a l O i l Products, h i s research group comprised 10 people. In a short time, h i s i n s p i r i n g l e a d e r s h i p , p r a c t i c a l experience, and canny f o r e s i g h t i n assigning problems y i e l d e d many d i s c o v e r i e s . His f i r s t major discovery i n the U.S. was the development of s i l i c o p h o s p h o r i c a c i d ( s o l i d phosphoric a c i d ) as a c a t a l y s t f o r hydrocarbon conversion. H 3 P O 4 + Kieselguhr

Δ " S o l i d Phosphoric A c i d "

I

SPA

I

Propylene was polymerized by means of t h i s c a t a l y s t to trimers to be blended with g a s o l i n e , and to tetramers to be used i n the manufacture of detergents.

S

C-C=C

P

A

»

(C H ) 3

6

4

S i l i c o p h o s p h o r i c a c i d was a l s o used i n copolymerization of butènes, which, followed by hydrogénation, y i e l d e d high-octane components f o r g a s o l i n e . C-C=C

+

C-C=C-C

I

c

C I

SPA Ni

c-c-c-c-c II c c

Polymerization r e a c t i o n was the f i r s t commercial c a t a l y t i c process introduced to the petroleum i n d u s t r y . I p a t i e f f can thus be considered the f a t h e r of petrochemistry. In the Second World War, t h i s c a t a l y s t was a l s o used i n the manufacture of cumene, a c r u c i a l component of high-grade f u e l f o r bombers·

+

C=C-C


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The discovery of conjunct polymerization, whereby hydrogen t r a n s f e r occurs between molecules of o l e f i n s , l e a d i n g to the formation of saturated hydrocarbons and polyenes, became the forerunner of the discovery of a l k y l a t i o n and i s o m e r i z a t i o n of p a r a f f i n s . During World War I I these processes were used f o r the manufacture of high octane a v i a t i o n gasoline to be used i n p u r s u i t planes, and p r e s e n t l y products from the a l k y l a t i o n react i o n assumed new importance as a major component of unleaded gasoline (Figure A).

Figure k. V. N. Ipatieff and Herman Pines, 1948.




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In the short p e r i o d between 1935 and 1939 I p a t i e f f coauthored over 50 research papers, and a p p l i e d f o r dozens of patents. He was e l e c t e d to the N a t i o n a l Academy of Sciences and received the coveted W i l l a r d Gibbs medal, and h i s achievements did not go unnoticed i n h i s n a t i v e land. In 1937, when he refused i n v i t a t i o n s of S t a l i n to r e t u r n to Russia, he was expelled from the Russian Academy of Sciences and deprived of h i s Soviet c i t i z e n s h i p . H i s son, a professor of chemistry at the Moscow U n i v e r s i t y , was made to denounce h i s f a t h e r i n a p u b l i c meeting, and I p a t i e f f s name was no longer c i t e d i n Russian chemical l i t e r a t u r e . At Northwestern, I p a t i e f f was an i n s p i r i n g teacher (Figure 5). H i s f i r s t graduate student, V l a d i m i r Haensel, invented the UOP platforming process.

Figure 5·

V. N. Ipatieff (1951). Taken by Chicago Sun-Times Photographer and. Entitled "The Thinker".



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I p a t i e f f was a man of charm and kindness, of modest d e s i r e s , and simple h a b i t s . He organized h i s work c a r e f u l l y and was annoyed by i n t e r f e r e n c e s i n h i s s c h e d u l e — a n d was most upset by h i s rare i l l n e s s e s . He hated to waste time, and prepared h i s l e c t u r e s and speeches weeks i n advance. He was g i f t e d with a f i n e sense of humor. When h i s o l d Swedish f r i e n d , Nobel, sent a congratulatory telegram f o r h i s 70th b i r t h d a y , he remarked, "From Nobel I get p r a i s e s but not p r i z e s . " He enjoyed s o c i a l o c c a s i o n s . He was a generous man, s e t t i n g up a loan fund to help impoverished graduate students. A number of h i s countrymen, f a c i n g the hardships of immigration i n o l d age, l i k e l y owed t h e i r very s u r v i v a l to him. These were matters, though, that I p a t i e f f p r e f e r r e d not to d i s c u s s . Cut o f f from h i s homeland and h i s c h i l d r e n (with whom he was forbidden to communicate), he s u f f e r e d g r e a t l y . He followed the events of the Second World War, e s p e c i a l l y Germany's i n v a s i o n of Russia, with profound concern. Two of h i s grandsons perished i n that war. On Nov. 29, 1952, w h i l e awaiting my a r r i v a l to d i s c u s s some l a b o r a t o r y problems, he died suddenly. Ipatieff l e f t a heritage of not only many innovations i n petroleum r e f i n i n g and p e t r o chemistry, but a l s o a h e r i t a g e of many students and a s s o c i a t e s who regarded working with I p a t i e f f as a r a r e p r i v i l e g e . His wife followed him 10 days l a t e r . F i f t e e n years t h e r e a f t e r , the I p a t i e f f High-Pressure and C a t a l y t i c Laboratory of Northwestern U n i v e r s i t y played host to a Centennial C e l e b r a t i o n of V l a d i m i r N i c o l a e v i t h I p a t i e f f . C a t a l y t i c experts from a l l over the world gathered f o r a weeklong symposium i n t r i b u t e to the f a t h e r of modern petrochemistry.

RECEIVED November 29,

1982


Heterogeneous Catalysis - ACS Publications - American Chemical

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