The Growth of Industrial Catalysis with the Platinum Metals€¦ · this sense gratis, it is evident that the systematic use of catalysts may lead to the most far-reaching advances

21

The Growth of Industrial Catalysis with the Platinum Metals

“ / / one considers that the deceleration o f reaction by catalytic means occurs without expenditure o f energy or material , and is in this sense gratis, it is evident that the systematic use o f catalysts may lead to the most far-reaching advances in technology. ”

W I L H E L M O S T W \ L I ) . 1 9 0 1

The discovery of the great activity of p latinum and palladium in the catalysis of chemical reactions and the early researches of the two Davys, Döbereiner, Faraday and others were reviewed in C hap ter 12, together with the famous patent of Peregrine Phillips of Bristol in 1831 and the early practical applications of Frédéric K uhlm ann in the production of sulphuric and nitric acids in his chemical works in France in 1838.

For almost forty years no progress was m ade in the further application of catalysis in industry. T he phenomenon was but little understood, while the chemical engineering techniques required to handle gases at high temperatures had not been developed. But as the dyestuffs industry grew the need for more concentrated sulphuric acid increased and two independent steps were taken in 1875. Then Dr. Rudolph Messel (1848—1920), who had come to London five years earlier after studying chemistry in Zürich, Heidelberg and T üb ingen to jo in William Stevens Squire (1835-1906), later to found the firm of Spencer C hapm an and Messel, devised a process of producing oleum by passing the vapour of ordinary sulphuric acid over platinised pumice at a red heat. T he patent was filed in Squire’s name only (1), and the process was put into operation, an account being given to the Chemical Society (2). Almost simultaneously a paper was published by Clemens W inkier (1838-1902), Professor of Chemistry at the Freiberg School of Mines, in which he proposed the use of platinised asbestos in what was virtually Peregrine Phillips method of employing sulphur dioxide and oxygen in stoichiometric proportions (3). W inkler did not pa ten t his process, but used it in a chemical works in Freiberg of which he was a director.

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“A History of Platinum and its Allied Metals”, by Donald McDonald and Leslie B. Hunt

© 1982 Johnson Matthey

R udolf T heophil Josef K nielsch 1854-1906

\ n a t iv e of O p p e ln in w h a t is now P o la n d , k n i e t s r h first b e c a m e a m e c h a n ic and th e n s tu d ied chem is try in B erl in . In 1884 he jo in ed (he B a d is c h e \ n i l i n u n d Soda F a b r ik a n d c a r r ie d ou t a long a n d success fu l inves tiga t ion on the p ro d u c t io n of s u l p h u r ic ac id by (he o x id a t io n of s u lp h u r d io x id e ov e r a p la t in u m ca ta lys t . His study o f v a ry in g con d i t io n s of t e m p e r a t u r e , th e r a te of flow o f the r e a c ta n t s a n d the po ison ing of the ca ta ly s t by a r se n ic a l f u m e s m a d e poss ib le th e la rge sca le p ro d u c t io n of ac id by th e con tac t p rocess w hich then b egan to s u p e r s e d e th e lead c h a m b e r m e th o d

P h o to g ra p h In rourt«*s\ of I ta ri ische Anilin ii ihI So d a Kahr ik

However, his method pointed the way for others until the researches of Rudolf Knietsch at the Badische Anilin und Soda Fabrik. In a lecture given to the Deutschen Chemischen Gesellschaft in 1901 (4) he reported an extensive series of investigations on the behaviour of platinum catalysts in varying conditions of temperature and showed clearly that the concept of using a stochiometric mixture of gases was fallacious. T h e contact process thus began to replace the lead chamber process (and so th e days of the p latinum boiler was also num bered) first in Germany and then in England and the United States. Very large quantities of platinum were consumed over a long period but during W orld W ar I the supply in Germany was interrupted and as a substitute vanadium pentoxide was used and began to be adopted in about 1926 by American acid manufacturers and later in England.

T he M anufacture o f Nitric A cidWhile the use of a platinum catalyst for the production of sulphuric acid became one of the few applications of p la t inum to fall away, a very different state of

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affairs has characterised the production of nitric acid and here p latinum is still in use in large quantities.

During the latter years of the nineteenth century discussion began to arise among m en of science who were interested in the broader issues of their subject on what later became known as “ T h e Nitrogen P roblem ”. Typical of the expositions which now and then reached even the public press was the Presidential Address given by Sir William Crookes to the British Association for the Advancement of Science at its Bristol meeting in September 1898 (5). Crookes was concerned to show that at the prevailing rate of increase of population the world’s supplies of wheat would soon prove insufficient, and that the land would not continue to produce the same yield year after year unless adequate quantities of nitrogenous m anure were ploughed back. He appealed to the chemist to help remove the fear of famine by establishing a means of fixing atmospheric nitrogen, since the only available source — Chile saltpetre — might be exhausted in a comparatively short period of years.

This problem, of obtaining from the unlimited supplies of uncombined nitrogen in the atmosphere those compounds — principally amm onia and nitric acid - required for agricultural needs, was soon intensified by the realisation in a num ber of European countries that a precisely similar need for assured supplies of nitric acid existed in the manufacture of explosives, and that in the event of war the Chile nitrates might well prove to be inaccessible.

This is not to say that such thoughts inspired governmental action in any part of Europe; they were, in fact, confined to but a handful of scientists who could forersee their countries’ long-term needs. O ne such m an was Professor Wilhelm Pfeffer, (1845-1920), the famous botanist of the University of Bonn who in 1901 expressed his concern about the need for supplies of fixed nitrogen to his friend in the University of Leipzig, Professor Wilhelm Ostwald. A t this time Ostwald had occupied the Chair of Chemistry at Leipzig for some fourteen years and had built up a school of physical chemistry, devoting much of his energy to investigating the effects of catalysts on chemical reactions. His response to Pfeffer’s representations was immediate; it was obviously his duty as a chemist to play his part in making his country independent of Chile saltpetre, and in obtaining nitric acid from other sources.

Two possible lines of investigation presented themselves. Either free nitrogen and oxygen from the air could be combined, or ammonia, then readily available from the gas industry, could be oxidised to give nitric acid. As it seemed more simple to re-combine nitrogen which was already fixed than to fix free nitrogen, Ostwald decided to give his attention to the oxidation of ammonia.

T he reaction was known, and Ostwald would have been well aware of the earlier work of Kuhlmann. It was clear to him that the theoretical basis of the ammonia oxidation reaction would have to be elucidated before it could be developed on a large scale, and experiments were begun by Dr. Eberhard Brauer, at that time O stw ald ’s private assistant. T h e first experiments were made using a clean glass tube only a few milimetres in diameter containing

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T h e h is to r ic a p p a r a t u s with w h ich O s tw a ld a n d B r a u e r first s tu d ie d th e ox id a t io n o f a m m o n i a o \ e r a p l a t i n u m ca ta ly s t to p r o d u c e n i t r ic ac id in th e I n ive rs i ty o f L e ipz ig in 1901. T h e in v es t ig a t io n sh o w e d th a t th e c o n v e r sion was p r a c t i c a b le a n d re la t ive ly s im p le b u t m an y p ro b le m s h a d to be so lved b e fo re a c o m m e rc ia l p rocess cou ld be d e \ e lo p ed

platinised asbestos. Ammonia a n d air were passed over the catalyst in known quantities and with known velocities, and it was at once clear that the conversion to nitric acid was practicable and relatively simple to carry out, a lthough some difficulties lay in the absorption of the reaction products. T he historic apparatus used at this stage is shown above.

T he first experiments using platinised asbestos gave only small yields and a platinum-lined tube proved little better. A new reaction tube was therefore made, consisting of a glass tube 2 m m in diam eter in which was coiled a strip of p latinum about 20 cm long. T he whole tube was heated to redness, and the first experiment gave a converison of m ore than 50 per cent, while increasing the gas velocity gave a converison of 85 p e r cent.

Investigations were then carried out on the effects of variations in the ammonia: air ratio, in the time of contact and in the tem perature of the catalyst. Thus were laid the foundations o f a technical process for producing nitric acid from ammonia, but the transla tion from idea to practice presented many problems before the project was b rought to fruition.

Ostwald filed patents for his procedure in 1902 (6) although his G erm an patent was disallowed on account of K u h lm an n ’s earlier disclosures.

A small factory was made available to O stw ald and Brauer, and here a pilot

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By 1904 a p ilo t sca le a m m o n i a o x id a t ion p la n t c o m p r is in g th r e e r e a c to r s had b een bu i l t in a sm a ll p o w d e r factory p u t a t O s tw a ld s d isp o s a l by th e D irec to r of th e G e r m a n E xplos ives C o m b in e . P o ro u s p l a t i n u m shee ts w e re used as the ca ta ly s ts , a yield of 75 p e r cen t of n i tr ic ac id was o b t a in e d , a n d it was dec ided to e re c t a l a rg e r p lan t to p ro d u c e 3 0 0 k i lo g ra m s of ac id a day

plant was developed. By 1904 the three converters illustrated above had been built and operated, and it was decided to erect a larger-scale plant at the Gewerkschaft des Steinkohlenbirgwerks Lothringen at Gerthe, near Bochum, to produce 300 kg per day of nitric acid.

This plant was brought into operation in M ay 1906 and fully proved the feasibility of the process. A larger-scale plant was then designed and built, and by the end of 1908 was producing some three tons of 53 per cent nitric acid per day.

T he catalyst used at this time consisted of a roll of corrugated p latinum strip about 2 cm wide and weighing about 50 g, heated initially by a hydrogen flame. T he life of the catalyst was no more than a m onth or six weeks. The disadvantages of the process included the relatively large am ount of platinum required per unit of acid produced, and the uncertainty of tem perature control of the catalyst, but improvements were not long wanting.

The P latinum G auze CatalystProfessor Karl Kaiser, of the Technische Hochschule, Charlottenburg, attacked the problem, and filed patents in 1909 covering the pre-heating of the air to 300

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or 400°C and the use of a layer, usually four in number, of platinum gauzes. He was the first to employ p latinum in the form of gauze, and it is a tribute to his experimental skill that the precise form of gauze he settled on - wire 0.06 millimetre diameter woven to 1050 mesh per square centimetre - is still very largely employed. By 1912 K aiser had a pilot plant in operation at Spandau, Berlin, but while this was inspected repeatedly by British, French and American industrialists, he failed to interest them in his process, although a plant was erected at Kharkov in Russia.

Further work was carried o u t by Nikodem Caro and Albert Frank at the Bayerische Stickstoffwerke. Several patents were filed during 1914, the process being based upon a single p la tinum gauze which was electrically heated. Progress was slow for a time, a n d numerous experimental plants failed, but the outbreak of war gave a much g rea ter urge to the project and by 1916 the picture had changed radically. The F ra n k and Caro converter had by then been engineered by the Berlin-Anhaltische M aschinenbau A.G. (BAMAG), who had constructed more than thirty plants , first for the supply of nitric oxide to lead chamber sulphuric acid plants a n d later for nitric acid production. T h e single platinum gauze was subsequently replaced by multiple gauzes, and the electrical heating was discontinued. This type of plant supplied all the nitric acid required for explosives in G erm any during the later years of the war. T he converter had a diameter of 20 inches, the catalyst consisting of a layer of three p latinum gauzes woven from 0.006 inch diameter wire of 80 mesh to the linear inch, operating at about 700°C.

A much greater catalyst life w as obtained in this design of plant, extending to six months provided that conditions were uniform and that the gases were free from impurities that might have a poisoning effect.

The Synthesis o f A m m oniaShortly after O s tw ald ’s development of the amm onia oxidation process the raw material began to become more readily available. T he same considerations on the great importance of the fixation of nitrogen prom pted Fritz H aber (1868-1934), then an assistant professor at the Karlsruhe Technische Hochschule, to investigate the catalytic formation of am m onia from its elements, nitrogen and hydrogen. This reaction had already been studied in 1881 by George Stillingfleet Johnson, a dem onstra tor in chemistry at K ing’s College, London, who obtained ammonia in small quantity by passing the two gases over heated platinum sponge (9), and O stw ald had given some consideration to the process in 1904, but H aber established that a successful process depended upon the reaction being carried out u n d e r high pressure and at a high temperature. T he investigation was taken over in 1909 by the Badische Anilin und Soda Fabrik who assigned Carl Bosch (1874-1940) to carry the project further. H aber had employed osmium as his cata lyst (10) but the commercial success of the process required a metal that w as both less expensive and available in greater

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quantity, and after some twenty thousand experiments by Alwin M ittasch (1869-1953), the head ofcatalyst research at BASF, aso lu tionw as finally arrived at with a mixture of iron and its oxides. Both H a b e r and Bosch were awarded Nobel Prizes for Chemistry, the latter commenting on the initial experiments at high pressures in the course of his address:

“ T h e two contact tubes, m ade by M annesm ann, had an operating life of eighty hours, then they burst. If we had filled them with osm ium instead of the new catalyst the entire world stock of this precious m etal, w hich we had by now bought, would have disappeared. ” (11)

The Production o f Nitric Acid in AmericaAt the beginning of the 1914 war the United States possessed no source of nitric acid other than Chile saltpetre, and it became distressingly evident that the nation was dependent upon a foreign country in this respect, while the production of nitric acid from this starting-point required large quantities of sulphuric acid already in short supply.

Cyanamide had been m anufactured at N iagara Falls since 1909, and in 1916 the first American plant for the oxidation of amm onia produced from cyanamide was established by the American Cyanam id Com pany at W arners, New Jersey. T he catalyst employed was a single platinum gauze, electrically heated. In the meantime, the ordnance department had decided to take action, and Dr. C. L. Parsons, of the Bureau of Mines, was asked to investigate E uropean methods for nitrogen fixation. As a result the American Cyanam id Com pany was requested, in 1917, to form a subsidiary company, Air Nitrates Corporation, to act as agent for the United States Government for the construction and operation of a plant at Muscle Shoals, Alabama, to produce 110,000 tons a year of ammonium nitrate. This plant comprised some seven hundred catalyst units each containing a single rectangular p latinum gauze woven from 0.003 inch diameter wire, 80 mesh, and heated electrically to 750°C. T h e total weight of p latinum was a little over 300 oz, and the loading ratio about 1 kg per daily ton of ammonia.

D evelop m en ts in A m m onia O xidation in Great BritainThere had been little or no commercial interest in nitrogen fixation in Great Britain before the outbreak of war in 1914, and throughout the w ar period the supply of nitrogen products for munitions depended almost entirely on shipments of Chilean nitrate.

There were, however, a num ber of attempts to make nitric acid by the oxidation of ammonia, either from gas-liquor or cyanamide. An O stw ald plant was set up at Dagenham Dock by the Nitrogen Products Com pany in 1916—1917, but never achieved successful operation. T he Gas Light and Coke Com pany developed a plant at Beckton using a pad of three or four flat p la tinum gauzes as catalyst, and attained an output of a ton of nitric acid per day.

A systematic investigation was undertaken, at the instigation of the Nitrogen

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S ir Eric Rideal I 8 9 0 - 1 9 7 4

E d u c a t e d a t T r in i t y C ol lege . C a m b r id g e . a n d th e n a t th e U n ivers i ty of B o n n . B id e a l s e rv e d in the Boyal E n g in e e r s in W o r ld W a r I b u t was in v a l id e d o u t in 1916 a n d th e n jo ined th e M u n i t i o n s I n v e n t i o n B o a rd to g e th e r w ith J . B. P a r t in g to n , J . A. M ark e r , H. C. G r e e n w o o d , E. B. M a x te d a n d o th e r s wi t h th e o b jec t of e s ta b l is h in g th e a m m o n i a o x id a t io n p rocess in E n g la n d . E a r l i e r , w h i le on leave f ro m F r a n c e , he h a d s tu d ied this r e a c t io n in th e I n s t i tu te of C h e m is t ry in L o n d o n . T h e p ro je c t , c a r r ie d out at U n iv e rs i ty Co l lege , L o n d o n , led to the c o n s t ru c t io n o f a su c cess fu l c o n v e r te r b u t on a very sm a ll scale. H is d i s t in g u i sh e d c a r e e r in c lu d e d m u c h i m p o r t a n t r e s e a r c h in ca ta lys is

Products Committee, by J. R. Partington, E. K. (later Sir Eric) Rideal and others and was carried out in the laboratory of the M unitions Inventions Departm ent (13). An effective design of converter was evolved, employing either an electrically heated pad with two gauzes or a thicker pad that was self- sustaining in temperature w hen reaction had been established. Somewhat similar converters were constructed by Brunner M ond & C om pany and by the United Alkali Company, both of w hom turned to Johnson M atthey for advice on the production of the catalyst gauzes.

Although it came too late to b e of service in the war, the decision taken in 1917 to erect a synthetic am m onia p lant using the Haber-Bosch process led directly to the building of the Billingham plant by Synthetic Amm onia and Nitrates Ltd. (now Imperial Chem ical Industries Ltd.). T h e am m onia plant first came into operation in D ecem ber 1923 and the nitric acid plant - tne first successful large-scale plant in th is country — during 1927. An account of the early years of this development h a s been given by A. W. Holmes (14).

Although the process remains unchanged in principle — and even in some details such as the mesh sizes of th e gauze pads - the size and complexity of the plant units has been tremendously increased.

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After the war th e work of the M unit ions Inven tion D e p a r tm e n t was ta k e n over by B ru n n e r M ond an d C om p an y ( l a te r to becom e p ar t of Im p er ia l Chem ical In d us tr ies ) an d this a tm osph e r ic p res su re am m o n ia oxida tion p lan t was insta l led at B il l ingham in 1927. T h e p la t in um gauzes were twenty inches in d ia m e te r , by co n tra s t with those now em ployed ru n n ing up to five m etres in d iam e te r

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T h e p la t in um gauze ca ta lyst, s u p p l i e d by J o h n s o n M a t t h e y . u se d in th e researches ca r r ied out for the Munitions Inven t io n D e p a r t m en t in 1916. M easuring only six inches by four inches, it com prised two g au ze s m o u n te d in an a lum in ium f r am e with si lver leads for the hea ting c u rren t



From the 50 grams of corrugated foil in an Ostwald unit, the weight of platinum in a single converter has steadily increased until it may now reach from 20 to 30 kilograms, while the diam eter of the rhodium -platinum gauzes, introduced in 1928 by E. F Du Pon t as an improvement on the pure platinum formerly used ( 15), can be as great as five metres.

The Manufacture o f H y d ro g e n C yanideAnother process, developed som e years later by Leonid Andrussow, like Ostwald a native of Riga, at the I.G. Farbenindustrie plant in M annheim , also makes use of woven gauzes of rhodium -pla tinum alloy to convert methane, amm onia and air to hydrogen cyanide (16). This is required in enormous quantities for the m anufacture of acrylic resins such as polymethyl methacrylate, known in Britain as Perspex, in America as Lucite and in Germ any as Plexiglas, and adiponitrile, an intermediate in the production of Nylon (17). O perating tem peratures in the process are appreciably higher than in ammonia oxidation plants, ranging up to 1200°C, so that the mechanical strength of rhodium-platinum at high tem peratures and its resistance to oxidation play an important role in add it ion to its catalytic activity.

Catalysis in the Organic C h em ica l IndustryT he wider adoption of catalytic reactions with the p latinum metals in the manufacture of organic chemicals, eventually to achieve immense significance in the pharmaceutical, dyestuffs, plastics and synthetic fibre industries, occurred much later than was the case w ith inorganic products. A great deal of the basic research had been carried out by th e beginning of the twentieth century and even before, but the transition into commercial applications was slow in development.

As early as 1874 Professor Prosper de Wilde of the University of Brussels discovered that acetylene could b e hydrogenated to ethylene and then to ethane over a platinum catalyst (18) while in 1894 Professor Paul Sabatier and his assistant the Abbé J e a n Baptiste Senderens (1856-1936) at the University of Toulouse published the first of their very numerous papers on catalysis (19). Sabatier had been intrigued by Ludw ig M o n d ’s discovery in 1890 of the reaction between nickel and carbon m onoxide (page 377) and in 1902 he and Senderens reduced carbon monoxide to m ethane over a nickel catalyst (20). By 1911 Sabatier had reported at length o n the m any hydrogenation and dehydrogenation reactions that could be carried out in the laboratory and he became the leading authority on catalysis of his time although he m ade no attempt to introduce any industrial processes.

F ine ly D iv id ed P latinum a n d P allad iumM uch of the early work involved the use of very finely divided metals, generally in a colloidal state. Carl Ludwig P aa l (1860-1935) Professor of Chemistry in the University of Erlangen and later in Leipzig, made a long series of studies on the

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Paul Sabatier 1854-1941

B o rn a t C a rc a s s o n n e , a f t e r s tu d y in g at th e E co le N o r m a le in P a r i s S a b a t i e r becam e a n assistant to Marcelin Berthelot a t th e C o l lege d e F ra n c e . In 1882 he m o v e d to T o u lo u s e , b e in g a p p o in t e d P ro f e s s o r of C h e m is t ry in 1884 a n d r e m a in in g th e r e for th e r e m a i n d e r of h is l i fe d e s p i te a n o f fe r o f a c h a i r at the S o r b o n n e in success ion to M oissan . H e was a p io n e e r in th e field o f c a ta ly s is a n d w as a w a r d e d th e N o b e l P r i z e in c h e m is try for this w o rk in 1912. His m an y p a p e r s o n th e s u b je c t w e re s u m m a r i s e d . to g e th e r w ith th e w o rk of o th e r s , in his b o o k . “ La C a ta ly s e en C h im ie O r g a n i q u e " \ p u b l i s h e d in 1913

preparation of colloidal platinum and palladium and of their effectiveness on catalytic reactions (21) while Aladar Skita (1876—1953), Professor of Chemistry at Karlsruhe, pursued similar investigations on the hydrogenation of aldehydes and ketones with colloidal platinum and palladium (22) and the two collaborated in 1909 in filing a patent for causing these reactions (23). But the use of colloidal preparations was not a practical proposition outside the laboratory because of the difficulty of separating them from the reaction products and attention turned to the so-called “ blacks” , a finely divided form of the metal containing an uncertain amount of oxygen. Platinum black had been discovered by Dobereiner in 1833 (page 222), although the product described by Zeise in 1827 (page 264) was possibly of the same nature, bu t a reliable method for its preparation was first devised by O scar Loew (1844—1941), a plant physiologist in Munich, in 1890 (24). His method was improved by Richard Willstatter (1872-1942) in 1912 while he was for a period Director of the Kaiser Wilhelm Institute after a long series of investigations on the hydrogenation of aromatics (25). Professor Gustave Vavon of the University of Nancy also carried out a massive research on the hydrogenation of aldehydes and ketones in the presence of platinum black, describing these in his doctoral thesis to the

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R oger A dam s 1889-1971

\ graduate of Harvard. Adams spent some time studying under Professor Richard ^ illstàtter at the Kaiser ^ ilhclrn Institute in Berlin and in 1916 he was appointed Professor of Chemistry at the I niversity of Illinois where, apart from intervals of government service during two world wars, he remained until his retirement. Under Vi illstàtter he had been engaged in the preparation of platinum black for use as a catalyst and on his return from the first war in 1919 he successfully developed a procedure for its production in a state of high activity and reliability. This useful catalyst still bears his name and is widely used, particularly in the pharmaceutical industry

University of Paris in 1914 (26), while Vladimir Ipatieff (1867—1952) in St. Petersburg, another prolific worker in catalysis, after a series of investigations with nickel, studied a number of catalytic reductions with palladium black in 1912(27).

At about this time Nicolai Dmitrievich Zelinsky (1861-1953) also began his long series of researches, converting cyclohexane into benzene with both platinum and palladium blacks as catalysts and continuing these investigations for many years (28).

During this early period, however, the platinum blacks often showed a low or a varying activity and it was not until 1919, when the problem was tackled by Professor Roger Adams who h a d spent some time under W illstatter at the Kaiser Wilhelm Institute, that a p roduct of uniform activity was obtained consistently. Searching for an active catalyst for organic reductions, Adam s and his students developed a successful procedure for what is still known as A dam s’ Platinum Oxide Catalyst (29). A n account of their work with comments by Professor Adams himself may b e found in Platinum M eta ls Review (30). This

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catalyst was at first prepared by individual workers in their laboratories, but before long it came into use in the pharm aceutical industry and the demand increased. Scaling up was undertaken by platinum refiners in the United States, while in England Johnson M atthey collaborated with M ay and Baker to develop a process for its preparation in relatively large batches for use in a variety of liquid phase hydrogenation reactions (31).

Supported P latinum and P allad iu m CatalystsThese early forms of finely divided platinum and palladium catalysts were, however, largely superseded by supported catalysts, more especially of palladium in the first place, to make more effective use of the metal and to enable a wider range of reaction conditions to be met. Among a great many materials used as supports, including alumina, asbestos and silica gel, the most generally useful has been activated charcoal, and palladium-on-charcoal catalysts have played an important part in low pressure liquid phase hydrogenation reactions in the pharmaceutical industry to produce vitamins, cortisone and dihydrostreptomycin among other products. T he ir usefulness, and also tha t of platinum-on-charcoal in one establishment, M erck of New Jersey, has been described by W. H. Jones (32).

The Growth o f C om m ercia l ProcessesSlowly processes based upon catalysis began to come into industrial use for the production in large quantities of chemicals that were otherwise difficult or impossible to produce, although not at first with p latinum metals catalysts. T he first major liquid phase processes were for the conversion of animal and vegetable oils into edible fats, generally with finely divided nickel catalysts.

In gas phase reactions the first recorded processes, as mentioned earlier, was devised by Sabatier and Sanderens in 1902 for the production of m ethane from carbon monoxide and hydrogen, also over a nickel catalyst (20) while, following up this work in 1923, a major step forward was m ade by Franz Fischer (1877-1935) and Hans Tropsch (1889-1935) at the Kaiser Wilhelm Institut fur Kohlenforschung at MCilheim in the Ruhr, in developing their well known synthesis of liquid hydrocarbons by the gasification of coal and by reacting the hydrogen and carbon monoxide produced in the presence of a catalyst, first of cobalt and later of iron (33).

But the great stimulus to the use of the p latinum metals as catalysts came when petroleum began to replace coal tar as the major source of organic chemicals, and with the realisation that the p latinum metals, a lthough more expensive initially, often displayed greater activity and made it possible to carry out commercially important reactions at appreciably lower tem peratures and pressures than those necessary with base metal catalysts. G reater product selectivity could be achieved, while the platinum metals could readily be recovered and recycled, making their use m uch more commercially attractive.

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T he Production o f High O ctane Fuels and A rom atic C hem icalsAs long ago as 1894 Francis Clifford Phillips (1850-1920), Professor of Chemistry at Western University in Allegheny, Pennsylvania - another researcher well in advance of industrial exploitation - studied the nature and constituents of the natural gas a n d petroleum found in his native state and carried out a long series of investigations on the oxidation of hydrocarbons over finely divided platinum, palladium , iridium, rhodium and osmium supported on asbestos (34).

Before World W ar II the catalytic reforming of petroleum to increase the octane rating of petrol was in troduced in Britain, the United States and Germany, using a molybdenum o n alumina catalyst, but this was found to be uneconomical and was superseded by a process developed by Universal Oil Products and known as “ Platform ing” (35). This was devised from the great expertise on catalysis built up in th e later thirties under the leadership of Ipatieff andT ropsch , both of whom had b y then jo ined U.O.P., and by one of Ipatieff’s first students at Northwestern University, Vladimir Haensel. T he process involved the reforming of c rude naphthas to aromatic hydrocarbons, particularly benzene, toluene a n d the xylenes, over a p latinum on alumina

V lad imi r HaenselBorn in Germany. Haensel received his early training in Moscow and then under the leading catalytic expert Professor Vladimir Ipatieff at Northwestern University in Elvaston, Illinois. He joined Universal Oil Products in 1937. working with Ipatieff who divided his time between teaching and directing research there for many years. His major contribution was the development of a platinum on alumina catalyst that made it possible to produce not only high octane petrol but also a range of aromatic hydrocarbons from crude petroleum. The process, known as Platforming. has been adopted on a world wide basis. In 1964 he was a p p o i n t e d V i c e - P r e s i d e n t and Director of Research at U.O.P., while in 1974 he was awarded the National Medal of Science by the U.S. Government for “ his outstanding research in the catalytic reforming of hydrocarbons which has greath enhanced the economic value of our petroleum natural resources".

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One of the early Platforming units commissioned by British Petroleum for the production of both high-octane petrol and a range of aromatic chemicals. The process, licensed from Universal Oil Products, employs a platinum-on-alumina catalyst and great numbers of plants of this type were erected in all parts of the world

catalyst, and apart from yielding the high octane petrol needed for modern automobile engines opened the way to the tremendous growth in the production of synthetic fibres, plastics, synthetic rubbers, insecticides and m any other chemical products.

Catalyst requirements were met by Universal Oil Products for many users, but in 1953 catalyst manufacturing facilities were set up in the United Kingdom by Universal-Matthey Products, a subsidiary company of Universal Oil Products and Johnson Matthey, in order to meet the growing dem and from European licensees of the Platforming process, while a few years later a similar plant was established in Cologne.

T he initiative taken by Universal Oil Products was quickly followed by others in the petroleum industry in developing broadly similar reforming processes employing platinum catalysts (36). In fact the response was enormous, and by the mid-1950s plants were being built in many countries of the world (37). Platinum reforming became one of the most versatile procedures available

399



to the oil industry - as well as a m ajo r user of p la tinum - and has continued to provide a wide range of intermediates for the chemical industries. T he benzene produced has many uses, including the manufacture of styrene and polystyrene, of cyclohexane for the production of Nylon (first discovered by W. H. Carothers whose doctoral thesis under Professor Roger Adam s dealt with the catalytic hydrogenation of aldehydes with p latinum black (29)), as well as of phenol for phenolic resins, dichlorobenzene for dystuffs and maleic anhydride for polyester resins. T he toluene produced finds extensive use as a solvent for nitrocellulose lacquers, while ortho-xylene yields phthalic anhydride for plasticisers, dyes and pigments and para-xylene is used to produce terephthalic acid for polyester fibres.

Thus the many types of synthetic materials that provide our fuel, our clothing and the many other items m ade from plastics depend for their production upon large-scale industrial processes in which the vital part is played by platinum.

R efer en ce s for C h ap ter 2 1

1 W. S. Squire, British Patent 3278 of 18752 R. Messel and W. S. Squire, Chemical News, 1876, 33, 1773 C. Winkler, Poly. J .( Dingier), 1875, 218, 128-1394 R. Knietsche. Ber. Deutsh. Chem. Gesellschaft. 1901, 34, 4069-4115; J . Soc. Chem. Ind.,

1902, 21, 172-1735 Sir William Crookes, British Association Report, 1898,3-386 W. Ostwald, British Patents 698 and 8300 of 1902; Chem. £ 'eitung, 1903, 27, 457-4587 K. Kaiser, German Patent 271,517; British Patent 20,325 of 1910; U.S. Patent

987,375 of 19118 A. Frank and N. Caro, German Patents 286991, 304269, 3038229 G. S. Johnson, J . Chem. Soc., 1881, 39, 128—13310 F. Haber, Elektrochem, 1910, 16, 244-246; Badische Anilin und Soda Fabrik,

German Patent 223408 of 191011 E. Färber, Nobel Prize Winners in Chemistry, New York, 1953, 12612 E.J. Pranke, Chem. and M et. Eng., 1918, 19, 395—39613 Ministry of Munitions, Munitions Invention Dept., H.M.S.O. London, 1919; J. R.

Partington and L. H. Parker, The Nitrogen Industry, London, 192314 A. W. Holmes, Platinum Metals Rev., 1959, 3, 2-815 E. I. Du Pont de Nemours, British Patent 306382 of 192816 L. Andrussow, German patent 549055 of 1932; angewand. Chem., 1935, 48,

593-59517 J. M. Pirie, Platinum Metals Rev., 1958, 2, 7-1 118 P. de Wilde, Berichte, 1874, 7, 352-357

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1920

21

2223242526272829

30313233343536

37

P. Sabatier and J. B. Senderens, Comptes rendus, 1897, 124, 616—618; 1358-1361 P. Sabatier and J. B. Senderens, Comptes rendus, 1902, 134, 514—516; 689-691C. L. Paal, Berichte, 1907, 40, 2201-2200; 1908, 41, 805-817; 2273-2282 A. Skita, Z- ongewand. Chem, 1913, 26. (i), 601-602A. Skita and C. Paal, German Patent 230724 of 1909 O. Loew, Berichte, 1890, 23, 289-290R. Willstätter and D. Hatt, Berichte, 1912, 45, 1464—1481G. Vavon, Ann. Chim, 1914, 1, 144—200 V. N. Ipatieff, Berichte, 1912, 45, 3218—3226 N. D. Zelinsky, J . Russian Phys. Chem. Soc., 1912, 44, 274—275V. Voorhees and R. Adams, J . Amer. Chem. Soc., 1922, 44, 1397—1405; W. H. Carothers and R. Adams, J . Amer. Chem. Soc., 1923, 45, 1071-1086 L. B. Hunt, Platinum Metals Rev., 1962, 6, 150-152D. H. O. John, Chem. and Ind., 1944,43, 256W. H. Jones, Platinum Metals Rev., 1958, 2, 86—89F. Fischer and H. Tropsch, Brennstoff Chem, 1923, 4, 276-285; 1924, 5, 201-208 F. C. Phillips, Am. C hem .J. 1894, 16, 163-187; 255-277; 340-365; 406-429 V. Haensel, U.S. Patent 2,479,109 of 1949S. W. Curry, Platinum Metals Rev., 1957, 1, 38-43; H. Connor, Platinum M etals Rev., 1961, 5, 9-12B. M. Glover, Platinum Metals Rev., 1962, 6, 86-91

401



Nikolai Semenovich Rurnakov

18 6 0 - 1941

O ne of the princ ipa l founders of the m odern p la tin um industry in the

I .S .S .R .. K urnakov was first a student and then in 1893 Professor of

Inorganic Chemistry in the M in in g Institu te in St. Petersburg. H is work

on the complex com pounds o f the p la tin um metals m aterially assisted

refining methods and on the death of Chugaev in 1922 he was appointed

Director of the P la tinum In stitu teP h o t o g ra p h b ' ro u rte s> o f ih e lal«* A c a d e m ic ia n

I. I. ( h e r n \ a e \ a m i P ro fe s s o r ( i e o r p e K a u f f m a n



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The Growth of Industrial Catalysis with the Platinum Metals€¦ · this sense gratis, it is evident that the systematic use of catalysts may lead to the most far-reaching advances