Pier, methanol synthesis

Walter Reppe also used his new base to expand the chemistry of acetylene. His first major breakthrough, in the summer of 1939, was the addition of carbon monoxide to acetylene in the presence of alcohols (or water) and a nickel catalyst to form acrylates. Carbon monoxide had attracted attention for many years as a readily available, cheap and reactive carbon compound. I.G. Farben employed it in the Pier methanol synthesis, Ruhrchemie used it in the Fischer-Tropsch synthetic petrol process, and Du Pont had carried out research on the addition of carbon monoxide to olefins at very high pressure and temperatures. Additional impetus for the use of carbon monoxide in acetylene chemistry was provided by the introduction of covered carbide furnaces at I.G. Farben s Knapsack plant in 1938, which permitted the collection of by-product carbon monoxide. The polymers of acrylic esters were already used for treating leather and for paint, but acrylic acid was made from ethylene oxide, and consequently was rather expensive. Reppe s process reached the pilot plant stage by 1945, and was subsequently used on a large scale by BASF and its American partners. 

For the Pier methanol synthesis, sec von Nagel, Methanol, Treibstoffe, pp. 7-11. For the Fischer-Tropsch process, see the references to oil-from-coal chemistry above (note 18) and Stokes, Opting for Oil, pp. 217-230. For the use of carbon monoxide at Du Pont, see Reader, Imperial Chemical Industries A History, volume 2, p. 321. 

The rapid rise in the production of methanol as chemical raw material first began in 1923 when the first large-scale synthesis plant was constructed by the Badische Anilin und Sodafabrik, Ludwigshafen (BASF). Based on the woik by Mittasch, M. Pier and his staff proved during test covering several years that iron is scarcely suitable as a catalyst for methanol production. On the contrary, it was established that iron must be carefully avoided in the production of methanol synthesis catalysts as its presence under the operating conditions applied to methanol synthesis leads to the formation of iron penta carbonyl which on its part resulted... 

Matthias Pier (1882-1965), a German chemist, worked with Emil Fischer and Walter Nernst during his studies. After WWI, he joined BASF and worked on ammonia and methanol synthesis. After BASF had purchased the patent on coal liquefaction from Bergius in 1925, he developed this process further. He found better and sulfur-resistant catalysts and increased the yield of fuels by arranging the process in two steps, liquid-phase hydrogenation and gas-phase hydrotreating of the intermediate product. Thus, the process is therefore mostly known as the Bergius-Pier process. 

High pressure technology transfer and diversification took many avenues, though most new innovations continued to appear from BASF. First, in 1923, was methanol production at the Leuna ammonia factory, and based on the work of Matthias Pier. BASF had patented a high pressure methanol process in 1914, but no further studies were carried out until after G. Patart in France applied for a similar patent (1921). In this case the same equipment could be used to manufacture ammonia or methanol, according to demand. Synthesis gas, the mixture of hydrogen and carbon monoxide, was used directly, without separation, to prepare methanol. In a similar way, isopropanol was manufactured under high pressures. 

In the Ludwigshafen Ammonia Laboratory located in Building 35 Pier resumed his high-pressure research, working for a time with Mittasch on the synthesis of ammonia and of methanol. The purpose of the ammonia experiments was to test the effectiveness of different iron catalysts at extremely high pressures, up to 1,000 atm as in the Claude process. Upon... 

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. 

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