Claims
- 1. A combined hydroformylation-aldolization process for converting, a C.sub.n olefin to a C.sub.2n+2 aldehyde comprising the steps of:
- (a) reacting said olefin with CO and H.sub.2 at a temperature in the range of about 50.degree. to 200.degree. C. and a total pressure in the range of about 15 to 2000 psia in a reaction zone containing a liquid reaction mixture comprising a base aldol condensation catalyst and a homogeneous, non-charged catalyst complex of the formula:
- [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g.(RhX.sub.n).sub.s
- wherein Ar is a substituted or unsubstituted C.sub.6 to C.sub.10 aromatic radical, Q is an unsubstituted or substituted C.sub.1 to C.sub.30 saturated open chain alkylene radical; R is an unsubstituted or monosubstituted C.sub.1 to C.sub.10 hydrocarbyl radical, X is an anion or organic ligand, excluding halogen, satisfying the valence and coordination sites of the metal, y is 1 to 6, g is 1 to 6 with the proviso that g times y is 1 to 6, n is 2 to 6, s is 1 to 3, said substituents on said hydrocarbyl radical, being chemically unreactive with materials used in and the products of the hydroformylation reaction, and
- (b) withdrawing said liquid reaction mixture from said reaction zone and recovering said C.sub.2n+2 aldehyde.
- 2. The process of claim 1 wherein said hydroformylation products further comprise hydrogenation products of said C.sub.2n+2 aldehydes.
- 3. The process of claim 1 wherein the H.sub.2 /CO ratio is greater than three, the ligand/Rh molar ratio is greater than 140 and wherein the process temperature is between 120.degree. to 175.degree. C.
- 4. The process of claim 1 wherein the catalyst complex is tris(2-trimethylsilylethyl diphenyl phosphine) rhodium carbonyl hydride.
- 5. The process of claim 1 wherein said liquid reaction mixture is a homogeneous phase.
- 6. The process of claim 1 wherein said aldol condensation catalyst is KOH present in about 0.05 to 0.5 weight percent of the total liquid reaction mixture.
- 7. The process of claim 1 wherein said liquid reaction mixture contains an ether-alcohol solvent.
- 8. The process of claim 1 wherein said catalyst is of the formula:
- {[Ph.sub.2 P(CH.sub.2).sub.m ].sub.y Si(CH.sub.3).sub.4-y }.sub.g Rh(CO)H
- wherein m is 2-14, Ph is phenyl, and y and g are as described above in claim 9.
- 9. The process of claim 1 wherein said olefin is a terminal olefin.
- 10. The process of claim 1 wherein said olefin is a mixture of butene-1 and cis- and trans-butene-2.
- 11. The process of claim 1 wherein said catalyst is of the formula:
- [[Ph.sub.2 P(CH.sub.2).sub.m ].sub.y Si(CH.sub.3).sub.4-y ].sub.g Rh(CO)H
- wherein m is 2-14, Ph is phenyl, y is 1 to 3 and g is 2 or 3.
- 12. The process of claim 1 wherein said olefin is a terminal olefin.
- 13. The process of claim 1 wherein said olefin is a mixture of butene-1 and cis- and trans-butene-2.
- 14. A combined hydroformylation-aldolization process for converting a C.sub.n olefin feed, said olefin being a terminal or internal olefin or mixture thereof, to a C.sub.2n+2 aldehyde comprising the steps of:
- (a) reacting said olefin with CO and H.sub.2 at a temperature in the range of about 120.degree. to 175.degree. C. and a total pressure in the range of about 15 to 2000 psia in a reaction zone containing a liquid reaction mixture comprising a base aldol condensation catalyst and a homogeneous, non-charged hydroformylation catalyst complex of the formula:
- [[Ar.sub.2 P(CH.sub.2).sub.m ].sub.y SiR.sub.4-y ].sub.3 Rh(CO)H
- wherein Ar is a substituted or unsubstituted C.sub.6 to C.sub.10 aromatic radical, R is an unsubstituted or monosubstituted C.sub.1 to C.sub.10 hydrocarbyl radical, m is 2 to 14, y is 1 to 4; said substituents on said aromatic radical, and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of a hydroformylation reaction, and
- (b) withdrawing said liquid reaction mixture from said reaction zone and recovering said C.sub.2n+2 aldehyde.
- 15. The process of claim 14 wherein said internal olefin reactant is in admixture with a hydrocarbon selected from the group consisting of terminal olefins, diolefins, C.sub.1 -C.sub.10 paraffinic hydrocarbons, aromatic hydrocarbons, or mixtures thereof.
- 16. The process of claim 14 wherein said process is carried out in a continuous recycle flash off mode of operation wherein said withdrawn liquid reaction mixture is further heated under reduced pressure to continuously recover product aldehyde and recovered catalyst is recirculated back to said liquid reaction mixture.
CROSS REFERENCE TO RELATED APPLICATIONS
This is a division of application Ser. No. 295,193, filed Aug. 21, 1981 which is a continuation-in-part application of U.S. Ser. No. 192,810 filed Oct. 1, 1980, which is a Rule 60 divisional of Ser. No. 11,238 filed Feb. 12, 1979 which is now U.S. Pat. No. 4,298,541, issued Nov. 3, 1981.
US Referenced Citations (10)
Foreign Referenced Citations (6)
Number |
Date |
Country |
WO801689 |
Feb 1980 |
WOX |
WO801691 |
Feb 1980 |
WOX |
WO801692 |
Feb 1980 |
WOX |
1342877 |
Jan 1974 |
GBX |
1419769 |
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GBX |
Divisions (2)
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Number |
Date |
Country |
Parent |
295193 |
Aug 1981 |
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Parent |
11238 |
Feb 1979 |
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Continuation in Parts (1)
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Number |
Date |
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Parent |
192810 |
Oct 1980 |
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