August, 1925
IA‘D USTRIAL A N D ENGINEERISG CHE-WISTRY
x.59
Synthetic Methanol Controversy We print here a statement made by the Badische Anilin und Soda Fabrit, originally printed in Chemiker-Zeitung, 59, 463 (1925). and later in the Chemical Trade Journal (London), June 5 , 1925. W e also gire the reply by M . Patart in the June 19 number of the same journal. What we print here, howeoer, has been translafedfrom the originals. which we were fortunafe enough to obtain.-EDIToR.
HE French chemist Patart has recently published an account of his work on the synthetic production of methanol from carbon monoxide and hydrogen. From t’hisreport, through which the details of his process first became known to the industrial world, and also to us, the foreign technical press [see Ind. Eng. Chem., 17, 430 (1925)] has concluded that our work, which led to the industrial synthesis of methanol and higher alcohols, followed the work of Patart and extended his results. We therefore wish to make the fpllowing statement: As early as 1913 we studied experimentally the hydrogenation of carbon monoxide under pressure, and established the fact, also recognized by Patart, that unlike hydrogenation a t ordinary pressure, which only produces methane, it is possible in this way to obtain liquid hydrocarbons, as well as alcohols, aldehydes, and so forth. Further work toward the perfection of this process, which was patented by us, soon had t o give way to the more urgent war problems, especially the conduction of the ammonia synthesis on a large scale, and was further delayed on account of the unfavorable political conditions following the war. As soon as possible we began new experiments, and in this as well as in other ways sought to effect the synthesis of methanol. I n 1922 appeared Patart’s patent on the synthetic production of alcohols, aldehydes, aliphatic and aromatic acids, etc. [French patent 540,543; patent application, 19211, which, as stated in his report, was the result, not of experiment, but of considerations similar t o those which led us t o our experiments and results of 1913. This patent has had no effect on our work, chiefly as it has not been possible t o produce methanol on an industrial scale with any of the catalysts named. Our own successful technical experiments with suitable contact masses, suitable container material, and suitable gases (absolutely necessary assumptions) began in 1922-23. (Our first revelant patents were granted in 1924.) Because of the experience gained in our previous work these experiments very quickly made it possible to try the process on a large scale (middle of 1923). Patart operated a small experimental plant for the first time early in 1923, and later-after his first experiments with his own catalysts failed, and because of which, as he says, he lost much time-using contact masses similar to ours he attained success. He himself specifically states, however, that the Badische succeeded in reaching industrial production much quicker than he.
The above-mentioned report in the foreign press is therefore incorrect. Furthermore, in our work efficient catalysts for the synthesis of methanol and its higher homologs, as well as other requirements for carrying on the work, were found for the first time, and are therefore the basis for the technical development of this synthesis. (Signed) BADISCHE ANILINUND SODA FABRIK
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0 the foregoing charges M. Patart, whom the abovementioned article in THISJOURNAL credited with the invention of the process for the synthetic production of methanol, by means of which the Badische has manufactured large quantities of this product and has recently imported it into the United States, replies as follows: (1) The Badische claims that the processes that it now uses are only a development of the processes patented by that company in 1913 [D. R. P. 293,787, dated March 8, 1913; 295,202, dated May 31, 1914; and 295,203, dated June 23, 19141. Now, if these patents speak of alcohols in general as secondary products of the reaction, there is no question of their covering
methanol, which is not even named. bloreover, Prof. Franz Fischer, director of the Kaiser Wilhelm Institut a t MiilheimRuhr, well known for his work on the subject, used these words in discussing the work of the Badische in 1913 and in the ten years following: These experiments have apparently been abandoned by the Badische, because, as was said t o one of us (Fischer), the catalytic process employed was not leading to the obtaining of a product whose chemical exploitation seemed realizable. We are able t o confirm this, for we have verified the fact that the product obtained by this process is very heterogeneous. [Byemstof-Chemie, 4, 276 (1923).1
(2) The Badische states that none of the catalysts mentioned in our patent of 1921 are suitable for the industrial synthesis of methanol.
To this we reply that the patent listed as catalysts suitable for this purpose “metals, their oxides, or their salts known as hydrogenating or oxidizing agents.” But Ullmann [Enzyklopadie von chemischen Technologie, Vol. VI, 1919, p. 6761 indicates as catalysts known as oxidizing agents the oxides of palladium, osmium, gold, silver, chromium, manganese, copper, cobalt, uranium, vanadium, tungsten, molybdenum, cerium, zirconium, thorium, titanium, and silicon. Now, in its patents (the only ones with which we are familiar a t the present time, because the German patents have not yet been published) the Badische mentions as contact masses for the synthesis of methanol the oxides of aluminium, magnesium, lead, bismuth, thallium, zinc, cadmium, copper, tin, antimony, silicon, boron, titanium, chromium, manganese, molybdenum, cerium, cobalt, osmium, and palladium. On the other hand, zinc and zinc oxide have been known since the work of Ipatiew [ Ber., 44, 3459 (19i1) 1 as active agents of catalytic hydrogenation. Most of the catalysts said t o be discovered by the Badische for the synthesis of methanol were therefore designated in our patent taken out eighteen months before the pretended discovery by the Badische. (3) According t o the Badische, that company was the first to specify the nature of the substances capable of forming apparatus suitable for the synthesis in question. But in our 1921 patent we did not a t any time specify the use of iron for making the apparatus for the catalysis. Far from that, for we indicated that the reaction chamber was to be constructed of “metal or any other appropriate substance,” and further, we even indicated that in the parts to be heated there should be used special metallic alloys made from “metals other than iron.” I t is hard to see, therefore, how the Badische can claim today, as it tries to do [French patent of September 2, 19241, to have patented the feature of “the complete exclusion of iron from the contact chamber.” Few claims are known which are so contrary to right and even to good sense.
(4) But there is still more. The Badische has the temerity to claim the paternity of the discovery of the nature of the gaseous mixtures used. It is precisely on this point that the Badische has run aground. As a matter of fact, in its patents taken out in 1913 and 1914 it was mistaken in choosing for the composition of the gaseous mixture a proportion of carbon monoxide greater than that of hydrogen; under these conditions methanol cannot be obtained, but, instead, chiefly oily liquids, insoluble or difficultly soluble in water, as the Badische recognizes now, but a long time after my 1921 patent, in which I indLcatedthat the proper proportion of the gaseous mixture to obtain methanol was two volumes of hydrogen and one volume of carbon monoxide. That, however, does not prevent the Badische from claiming right to patent today [French Patent 571,355, October 1, 19231 the composition which I indicated in August, 1921.
It cannot be denied that the Badische has been the first to place upon the market synthetic methanol, made, however, by a process borrowed from another. This company has succeeded in accomplishing this, thanks to the almost unique facilities which it possesses. But that does not give it a right to claim credit for a process to which it has no right. (Signed) GEORCESPATART
