| 摘要 |
1371795 Cobalt carbonyl; iron carbonyl cobaltate DAICEL Ltd 13 Sept 1971 [14 Sept 1970 (2)] 42557/71 Heading C1A [Also in Division C2] Cobalt is recovered as cobalt carbonyl from the product of an "oxo" reaction in which cobalt is used as the catalyst by treating the product with a material containing iron, which material is selected from metallic iron, iron oxides, and hydroxides and iron salts of weak acids, the contact taking place in the presence of water, carbon monoxide and hydrogen whereby the cobalt moves into the aqueous phase as an iron carbonyl cobaltate, this aqueous phase is separated from the organic phase, and the cobalt carbonyl regenerated by treating the aqueous phase with a mineral or organic acid. If desired, the carbonyl may be obtained as the hydrocarbonyl by passing an inert gas through the aqueous phase, and dissolving the hydrocarbonyl thereby carried away by treating the gas with an organic solvent or "oxo" reactant, or the carbonyl may be extracted by a suitable organic liquid. The solution of carbonyl so obtained may be recycled as catalyst to the oxo reaction. The iron containing material may be a ferrous hydroxide containing mixture obtained by mixing an aqueous soln. of a ferrous salt of a strong acid with an alkaline metal or alkaline earth metal hydroxide. The iron-containing material may also be wrought iron, Raney iron, reduced iron, undeveloped Raney iron, or the carbonates, bicarbonates, sulphide, naphthenate, lactate or acetylacetonate of iron. Preferably the amount of iron used is at least equivalent to the amount of cobalt in the starting mixture. The amount of water used may be from 10% to 500% by volume based on the volume of the initial oxo product. The extraction may be carried out at a pressure of 10-500 kg./cm.<2> gauge, preferably 50 to 300 kg./cm.<2> gauge of a mixed gas of CO and H2 in a ratio of 1 : 1 to 1 : 2 at a temp. of 60-200‹ C., preferably 100‹ to 170‹ C. The mineral acid used may be sulphuric acid, hydrochloric acid or phosphoric acid, and the organic acid may be trichloroacetic acid or p-toluene sulphonic acid. In Example 1, butyraldehyde is obtained by using propylene as reactant and dicobalt octacarbonyl as catalyst in an "oxo-reaction". Cobalt is removed from the productusing the above process. |
