Carbonylation Operations and Economic Aspects of Their Reaction Products

Industrial Carbonylation Operations and Economic Aspects of Their Reaction Products 

Although numerous carbonyl compounds available by Reppe reactions are of high economic interest, for instance the acrylates and saturated carboxylic acids, capacities of carbonylation processes are much lower than capacities of hydroformylation processes. In many cases it may be due to the fact that the same products can be obtained by more attractive processes starting with easily available olefins. 

Actual operating capacities of Reppe carbonylation processes are difficult to estimate since only a few data are available in the literature. However, it is known that some of the syntheses are carried out on an industrial scale, e. g. the synthesis of acrylates from acetylene, carbon monoxide and alcohols (BASF) [1004, 1005], the acetic acid synthesis from methanol and carbon monoxide and the synthesis of higher molecular weight saturated carboxylic acids from olefins, carbon monoxide and water. Propionic acid (30,000 tons/year) and to a smaller extent heptadecanoic dicarboxylic acid are manufactured via the carbonylation route at BASF. Butanol is made from propylene in Japan [1003, 1004]. 

A variation of the conventional acrylate synthesis was developed by Rohm and Haas in the USA [578, 579] and Montecatini in Italy [580]. This process tries to combine the advantages of both the pressureless stoichiometric procedure and the low Ni(CO)4 catalyst concentration of the catalytic procedure. 

At atmospheric pressure and temperatures of 30-50 °C acrylates are obtained in yields of 80-90% by this method of operation. Only 15% of the required carbon monoxide originates from Ni(CO)4. 

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