Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1989-10-25
1991-08-20
Lone, Werren B.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568454, 568882, C07C 4550
Patent
active
050416855
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
The present invention concerns a procedure for producing alcohols and aldehydes from alkenes and synthesis gases.
Oxygen containing compounds such as alcohols and aldehydes are generally produced by hydroformylation processes. The catalysts of industrial processes are typically homogeneous rhodium or cobalt carbonyls or phosphines. Heterogeneous catalysts can be produced by binding a metal compound on a fixed organic or inorganic carrier, whereby certain advantages are gained. The heterogeneous catalyst is easy and advantageous to separate from the products, which is specifically advantageous in using expensive rhodium catalysts. The heterogeneous catalyst is also thermally more stable than the homogeneous catalyst and causes less corrosion. In addition, the metal compound and the carrier may have useful combined effects. The processes of the homogeneous catalysts are however more specific and repeatable.
Metal cluster compounds are provided with advantageous characteristic features as precursors to catalysts because their specific structures as catalysts enable them to have better activities and particularly selectivities in comparison with simple metal complexes. The greatest difficulty is, however, the instability of metal cluster compounds. Advantages of heterogeneous cluster catalysts are lack of halides (a halide can be a catalytic toxic agent and cause aggregation and sintration), and provision of exact combination.
In the Finnish Patent No. 69620 is disclosed a catalyst for producing hydrogen gas from carbon monoxide and water (transfer reaction of aqueous gas). The catalyst is produced from the group VIII metal carbonyls and heterocyclic base. The metal carbonyl of the group is Ru.sub.3 (CO).sub.12, FeRu.sub.2 (CO).sub.12, Fe.sub.2 Ru(CO).sub.12, or their derivative M.sub.3 (CO).sub.12- L.sub.x, in which M is Ru or Fe, x is 1 or 2, and L is a trialkyl or triaryl phosphine or phosphite. The heterocyclic base used is a 2,2'-bipyridine or 1,10 phenantroline.
SUMMARY OF THE INVENTION
As taught by the invention, the dissolvent containing the metal carbonyl compound and heterocyclic base was refluxed at 80.degree. C., whereby an active complex was produced in the transfer reaction of the aqueous gas. The heterogeneous catalyst was produced directly on the surface of the carrier by heating at 100.degree. C. protective gas or vacuum silicon gel in which cluster compound and base were impregnated. Thereby was produced a dark blue active catalyst. Advantages of the catalyst of the invention are outstanding activity and stability whereas a disadvantage sensitivity to air.
As taught by the invention, it has been found that from the above described metal cluster base system a new catalyst can be synthetized for producing alcohols or aldehydes from alkenes and synthesis gas by means of a hydroformylation reaction. Thus, the procedure of the invention for producing alcohols or aldehydes from alkenes and synthesis gas by means of hydroformylation reaction is characterized in that a gas mixture containing alkene, hydrogen and carbon monoxide is made to react at over 100.degree. C. in the presence of the heterogenic catalyst system, comprising a solid catalyst compound produced from a cluster compound Ru.sub.3 (CO).sub.12 and from a heterogeneous base in a suspension, or bound on the surface of a solid carrier substance.
In the procedure of the invention is gained the surprising advantage that alcohols are produced in the hydroformylation at a high selectivity rate. In certain instances, from alkenes are produced almost exclusively alcohols. This is a very great improvement in comparison with conventional hydroformylation catalysts which merely yield either aldehydes or mixtures of aldehydes and alcohols, and thus require an extra processing phase for hydrating aldehydes into alcohols. In addition, with the procedure of the invention the desired direct-chain alcohol is obtained in a remarkably selective manner. The activity of the catalyst is also significant in hydroformylation of m
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patent: 4469895 (1984-09-01), Knifton et al.
Journal of Molecular Catalysis, 29 (1985) pp. 77-98.
Alvila Leila
Krause Outi
Pakkanen Tapani
Venalainen Tapani
Lone Werren B.
Neste Oy
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