Stable long-term method for producing C5-aldehydes

Patent metadata

Field	Value
Publication number	US-9272973-B2
Application number	US-201314435052-A
Country	US
Kind code	B2
Filing date	Sep 27, 2013
Priority date	Oct 12, 2012
Publication date	Mar 1, 2016
Grant date	Mar 1, 2016

Abstract

The invention relates to a process for preparing aldehydes having five carbon atoms, in which an input mixture containing 10% by weight to 50% by weight of linear butenes and less than 5% by weight of 1-butene is hydroformylated with synthesis gas in the presence of a catalyst system comprising rhodium and at least one bisphosphite ligand, wherein the hydroformylation is effected in a reactor from which, over an operating period, a cycle gas containing at least a portion of the products and unconverted reactants from the hydroformylation is continuously drawn off and partly condensed, and uncondensed components of the cycle gas are recycled into the reactor, and wherein, after the operating period has expired, the hydroformylation is stopped, the reactor is freed of reaction residues and the hydroformylation is restarted. It is based on the problem of making such a process more economically viable. The problem is solved by using a bisphosphite of the formula (1) and/or (2) as ligand, extending the operating period to more than 8000 h, and not separating solid reaction residues out of the reactor during the course of the operating period.

First claim

The invention claimed is:

1. A process comprising preparing aldehydes having five carbon atoms, in which an input mixture comprising 10% by weight to 50% by weight of linear butenes and less than 5% by weight of 1-butene is hydroformylated with synthesis gas in the presence of a catalyst system comprising rhodium and at least one bisphosphite ligand, wherein the hydroformylation is effected in a reactor from which, over an operating period, a cycle gas comprising at least a portion of products and unconverted reactants from the hydroformylation is continuously drawn off and partly condensed, and uncondensed components of the cycle gas are recycled into the reactor, and wherein, after the operating period has expired, the hydroformylation is stopped, the reactor is freed of reaction residues and the hydroformylation is restarted,
wherein
the operating period lasts for at least 8000 h,
there is no separation of solid reaction residues out of the reactor during the course of the operating period,
and the catalyst system comprises the bisphosphite ligand of formula (1) and/or the bisphosphite ligand of formula (2):

2. The process according to claim 1 ,
wherein
the catalyst system comprises both the bisphosphite ligand of the formula (1) and the bisphosphite ligand of the formula (2).

3. The process according to claim 2 ,
wherein
the molar ratio of the bisphosphite ligands of the formula (1) to the bisphosphite ligands of the formula (2) in the hydroformylation is between 10 and 30.

4. The process according to any of claim 1 or 2 ,
wherein
the hydroformylation is conducted in the presence of an organic amine of formula (3):

in which Ra, Rb, Re, Rd, Re and Rf are identical or different hydrocarbyl radicals which may also be joined to one another.

5. The process according to claim 4 ,
wherein
the organic amine has at least one 2,2,6,6-tetramethylpiperidine unit.

6. The process according to claim 5 ,
wherein the organic amine is a di-4-(2,2,6,6-tetramethylpiperidinyl) sebacate.

7. The process according to claim 1 ,
wherein
the hydroformylation is conducted in the presence of isononyl benzoate.

8. The process according to claim 1 ,
wherein
the cycle gas is partly condensed at a condensation temperature of 50° C. to 90° C.

9. The process according to claim 1 ,
wherein
the operating period is 12 000 h or more.

10. The process according to claim 1 ,
wherein
the input mixture comprises 10% to 50% by weight of linear butenes, less than 2% by weight of 1-butene and at least 50% by weight of butanes.

11. The process according to claim 1 ,
wherein
the hydroformylation is conducted under the following reaction conditions:
Pressure: 1 MPa to 20 MPa;
Temperature: 70° C. to 150° C.;
Rhodium concentration: 1 ppm by weight to 1000 ppm by weight;
Ligand/rhodium ratio: 1 to 100.

12. The process according to claim 8 , wherein the condensation temperature is between 65° C. and 75° C.

13. The process according to claim 8 , wherein the condensation temperature is 70° C.

Assignees

• Fridag Dirk
• Franke Robert
• Hess Dieter
• Schwarz Markus
• Dyballa Katrin Marie
• Lueken Hans-Gerd
• Hamers Bart
• Ernst Uwe
• Evonik Industries Ag

Inventors

• Fridag Dirk
• Franke Robert
• Hess Dieter
• Schwarz Markus
• Dyballa Katrin Marie
• Lueken Hans-Gerd
• Hamers Bart
• Ernst Uwe

Classifications

• B01J31/0271

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0231 · CPC title

• B01J31/0209

  Esters of carboxylic or carbonic acids · CPC title

• C07C45/505 Primary

  Asymmetric hydroformylation · CPC title

• C07C67/38

  by addition to an unsaturated carbon-to-carbon bond · CPC title

• B01J2531/822

  Rhodium · CPC title