Historic Developments in Heterogeneous Carbon Monoxide Hydrogenation

Historic Developments in Heterogeneous Carbon Monoxide Hydrogenation 

Tlte first reports on heterogeneous CO hydrogenation over nickel catalysis to give methane were made in 1902 by Sabatier and Senderens. The reaction was carried out at normal pressure at 200-300 C [16]. 

Tlte synthesis of liquid hydrocarbons was first reported in patents from BASF in 1913. Alkali activated Co/Os catalysts were used at pressures over 100 bar and temperatures exceeding 300 C. The products obtained consisted of paraffins, olefins, and oxygenated products (I ). Tlte continuation of these studies led to the development of the methanol synthesis. The first commercial plant went on stream in 1923. 

The classical experiments of F. Fischer and H. Trupsch date back to 1922, when the CO hydrogenation over alkalized iron catalysis at high pressures (150 bar) and temperatures (400-4S0 C) was found to yield oxygen-containing products ( Synihol ) I8]. 

The introduction of iron-zinc catalysts led to the low pressure nthesis of liquid and solid hydrocarbons from CO/Hj in 1925 [19. 20. However, it was found that these catalysts were deactivated rapidly and thus further investigations concentrated on nickel and cobalt catalysts. They led to the introduction of a standardized cobalt-based catalyst for llic normal-pressure synthesis of mainly saturated hydrocarbons at temperatures below 200 C. In 1936, the first four commercial plants went on stream. Until 1945 the Fischer-Tropscit synthesis was carried out in nine plants in Germany, one plant in France, four plants in Japan and one plant in Manchuria. The total capacity amounted to approximately one million tons of hydrocarbons per year in 1943. The catalysts used consisted of Co (1(X) parts), ThO (5 parts). MgO (8 parts), and kieselgur (200 parts) and were prepared by precipitation of the nitrates. These catalysts were used in fixed-bed reactors at normal or medium pressures ( 10 bar) and produced mainly saturated straight hain hydrocarbons. The product obtained consisted of 46% gasoline. 23% diesel oil, 3% lubricating oil and 28% waxes (3.15). 

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