BASF ammonia process

In 1913, the same year as the first comnjercial ammonia process was launched, BASF began initial tests of a synthesis of methanol from pressurized H2/CO mixtures, leading to the first plant for the production of synthetic methanol (eq 1.1-10) at Leuna in Germany in 1923 [147,148]. Patart in France later claimed prior invention [149,150]. 

Quoted in Max Appl, The Haber-Bosch process and the development of chemical engineering, in W.F. Furter, ed., A Century of Chemical Engineering (New York Plenum, 1982), pp. 29-53, on p. 39. Appl, former head of the BASF ammonia department, provides an excellent overview of the technical development of the Haber-Bosch process. For work on catalysts see also Alwin Mittasch, Geschichte der Ammoniaksynthese t n C m. Verlag Chemie, 1951). 

It was mainly the BASF reticence to license the ammonia process, or release details, that led to the development of significant alternative high pressure ammonia processes, particularly in France, Italy and the United States, and competition from companies anxious to export that technology. 

BASF owns processes for the production of synthetic ammonia, which are used in its works at Oppau and Merseburg. BASF has taken out various patents in France to protect these processes. The French government, which desires to use and carry out these patents and processes in France, has regarded it as expedient, to this end, to secure the voluntary cooperation of BASF in connection with the utilization both of said patents and processes and of the keys to the industrial secrets which are necessary or useful for the purposes of manufacture and operation, and the use of more recent improvements or those which are still at the development stage. 

Given that the BASF ammonia works capacity remained small and that little experience had been gained with the Haber-Bosch process, Emil Fischer considered it unavoidable in October 1914 that cyanamide production also be developed on a massive scale in addition to the BASF-ammonia in Oppau. Caro agreed in principle, but because the Trostberg works could not be expanded without further ado because of their dependence on the existing water power there, he insisted on the condition that new electrical plants be built in order to supply the necessary power for cyanamide production elsewhere. Fischer established immediate contact between him and Hugo Stinnes, who had an ulterior motive to join with the constellation of interests around Caro, since the enterprise could prove lucrative if it drew on the incompletely exploited power from his Rheinisch-Westfalische Elektrizitatswerk AG. ... 

In the United States, a subsidiary of the DuPont Company, Lazote, Inc., made synthetic methanol at Belle, West Virginia. The Belle operation was part of the ammonia plant at the site. The methanol production was actually a step in the ammonia process for removing carbon monoxide, which was an impurity in the ammonia synthesis gas. Commercial Solvents was the first to employ the high-pressure synthesis process, developed by BASF, in the United States. The plant, located in Peoria, lUinois, began operation a few months after the Lazote plant at Belle. The Commercial Solvents plant used an off-gas from a fermentation operation. The off-gas contained carbon dioxide and hydrogen from the production of butanol from corn. This first of a kind plant in the United States was rated at about 4000 t per year. 

The Haber-Bosch ammonia synthesis process led to similar developments in other European countries and the US. As a result, many other commercial processes were being operated during the 1920s. Production rates were very small compared with modem plants but an extremely wide range of operating conditions was introduced together with a number of different catalysts. Despite these initial differences, most plants built in recent years still operate with more or less the same conditions as those chosen for the first BASF process. Some of the early ammonia processes are listed in Table 10.3. 

Subsequently, patents covering the conversion of synthesis gas to complex mixtures of organic oxygen compoimds, including methanol, were issued to BASF during 1913. This followed work by Mittasch and Schneider. Full-scale production of methanol was not attempted, however, imtil 1923. By that time high-pressure equipment had been in operation for several years in the new ammonia process. The methanol process was developed by Piers and the plant, built at Leima, used mixed zinc oxide-chromic oxide catalyst. The use of metallic iron for the internal parts of the reactor was avoided to prevent the formation of the volatile iron penlacarbonyl. The would have decomposed on the surface of the catalyst, to deposit finely divided iron metal, which in turn would have promoted the exothermic formation of methane. 

However, BASF developed a two-step process (25). After methyl formate [107-31-3] became available in satisfactory yields at high pressure and low temperatures, its conversion to formamide by reaction with ammonia gave a product of improved quaUty and yield in comparison with the earlier direct synthesis. 

To convert N2 and H2 into ammonia at a reasonable scale, flow reactors are needed that can be operated at high pressures. Until then, high-pressure reactions were mainly carried out in batch processes. Carl Bosch at BASF developed the technology that enabled scaling up to several tons of ammonia per day at 300 bar. 

Five years after Haber patented his process, BASF opened its nitrogenfixing ammonia factory in 1913. The Haber-Bosch process, as it is now... 

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