Recovery of high-boiling aldehydes from rhodium-catalyzed hydroformylation processes

• US 5,138,101 A
• Filed: 07/19/1991
• Issued: 08/11/1992
• Est. Priority Date: 07/19/1991
• Status: Expired due to Term

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Kodak Company
• Inventors: Devon, Thomas J.
• Primary Examiner(s): LONE, WERREN
• Application Number:
  US07/732,898
• Time in Patent Office: 389 Days
• Field of Search: 568/492, 568/454, 568/451
• US Class Current: 568/492
• CPC Class Codes: C07C 45/50 by oxo-reactions
• CPC Class Codes: C07C 45/80 by liquid-liquid treatment
• CPC Class Codes: C07C 47/12 containing more than one —CHO group
• CPC Class Codes: C07C 47/21 with only carbon-to-carbon double bonds as unsaturation
• CPC Class Codes: C07C 47/225 containing rings other than six-membered aromatic rings
• CPC Class Codes: C07C 47/32 with a six-membered ring
• CPC Class Codes: C07C 47/33 with a seven- to twelve-membered ring
• CPC Class Codes: C07C 47/347 having a —CHO group on a condensed ring system
• CPC Class Codes: C07C 47/43 with a seven- to twelve-membered ring
• CPC Class Codes: C07C 47/445 containing a condensed ring system

Abstract

Disclosed is an extraction process for the recovery of high-boiling aldehydes produced by the rhodium-catalyzed hydroformylation of olefins in the presence of a hydroformylation solvent. The extraction process involves intimately contacting a hydroformylation product solution comprising (i) a high-boiling aldehyde, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent with an extraction solution comprising a primary alkanol and water to form a 2-phase mixture. The phases are separated to obtain a hydroformylation solvent phase containing catalyst components and an alkanol/water phase containing the high-boiling aldehyde.

Claims

1. Process for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) a high-boiling aldehyde, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from the group consisting of alkanes having about 5 to 20 carbon atoms, benzene, toluene, xylene isomers, tetrahydronaphthalene, decahydronaphthalene and dialkyl benzenedicarboxylate esters, by the steps of:

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising a primary alkanol and water to form a 2-phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) an alkanol/water phase containing the high-boiling aldehyde.

2. Process according to claim 1 for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) an aldehyde having a boiling point of at least 125°

C. at atmospheric pressure, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent by the steps of;

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising a primary alkanol having 1 to 3 carbon atoms and water to form a 2 phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) an alkanol/water phase containing the aldehyde;

wherein the volume ratio of primary alkanol to water of the extraction solution is about 20;

1 to 1;

20 and the difference between the densities of the hydroformylation product solution and the extraction solution is at least 0.02 g/mL.

3. Process for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) an aldehyde having a boiling point of at least 125°

C., (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from alkanes having about 5 to 20 carbon atoms, alkyl-substituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, and decahydronaphthalene comprising the steps of;

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising methanol and water at a temperature of about 20 to 60°

C. to form a 2 phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) a methanol/water phase containing the aldehyde;

wherein the volume ratio of methanol to water of the extraction solution is about 5;

1 to 1;

1 and the difference between the densities of the hydroformylation product solution and the extraction solution is at least 0.05 g/mL.

4. Process according to claim 3 wherein the process includes (i) heating the methanol/water of step (2)(b) to vaporize at least 50 weight percent of the methanol and form a liquid phase of the aldehyde and (ii) separating the aldehyde from the liquid phase.

5. Process according to claim 3 wherein the aldehyde has the general formula:

##STR5## wherein R¹ is straight or branched chain alkyl of about 5 to 8 carbon atoms;

R² is straight or branched chain alkylene having about 2 to 18 carbon atoms; and

R³ is hydroxy, alkoxy of up to about 4 carbon atoms, alkanoyloxy of up to about 4 carbon atoms, carboxyl or alkoxycarbonyl of 2 to about 10 carbon atoms.

6. Process according to claim 3 wherein the aldehyde has the general formula ##STR6## wherein R⁴ is straight or branched chain alkylene having about 5 to 20 carbon atoms.

7. Process according to claim 3 wherein the aldehyde has the general formula ##STR7## wherein R⁵ is cycloalkylene having about 5 to 12 carbon atoms;

and

R⁶ is formyl, formylethyl, carboxyl or alkoxy carbonyl of 2 to about 10 carbon atoms.

8. Process according to claim 3 wherein the aldehyde is selected from decanedials, 4-(2-formylethyl)cyclohexanecarboxaldehyde, 1,4-cyclohexanedicarboxaldehyde, 4-formylcyclohexanecarboxylic acid, dimethyl 4-formylcyclohexanedicarboxylate, 1,4-cyclooctanedicarboxaldehyde, 1,5,9-cyclododecanetricarboxaldehyde, 3-(5,5-dimethyl-1,3-dioxanyl) propionaldehyde, 2-(formylnorbornanyl)acetaldehyde.

9. Process for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) a high-boiling aldehyde, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected form the group consisting of alkanes having about 5 to 20 carbon atoms, benzene, toluene, xylene isomers, alkyl-substituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, decahydronaphthalene and dialkyl benzenedicarboxylate esters, by the steps of:

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising a primary alkanol, water and a salt of a carboxylic acid to form a 2-phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) an alkanol/water phase containing the high-boiling aldehyde.

10. Process according to claim 9 for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) an aldehyde having a boiling point of at least 125°

C., (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent by the steps of;

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising a primary alkanol having 1 to 3 carbon atoms, water and an alkali metal salt of a carboxylic acid to form a 2-phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) an alkanol/water phase containing the aldehyde;

wherein the volume ratio of primary alkanol to water of the extraction solution is about 20;

1 to 1;

20 and the difference between the densities of the hydroformylation product solution and the extraction solution is at least 0.05 g/mL.

11. Process for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) an aldehyde having a boiling point of at least 125°

C., (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from alkanes having about 5 to 20 carbon atoms, alkyl-substituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, and decahydronaphthalene comprising the steps of;

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising methanol, water and 1 to 5000 ppm of an alkali metal salt of a carboxylic acid having 4 to 30 carbon atoms at a temperature of about 20°

to 60°

C. to form a 2-phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) an methanol/water phase containing the aldehyde;

wherein the volume ratio of methanol to water of the extraction solution is about 5;

1 to 1;

1 and the difference between the densities of the hydroformylation product solution and the extraction solution is at least 0.05 g/mL.

12. Process according to claim 11 wherein the process includes (i) heating the methanol/water of step (2)(b) to vaporize at least 50 weight percent of the methanol and form a liquid phase of the aldehyde and (ii) separating the aldehyde from the liquid phase.

13. Process according to claim 11 wherein the extraction solution comprises methanol, water and about 10 to 1400 ppm of an alkali metal salt of a carboxylic acid having about 8 to 18 carbon atoms and the aldehyde has the general formula:

##STR8## wherein R¹ is straight or branched chain alkyl of about 5 to 8 carbon atoms;

R² is straight or branched chain alkylene having about 2 to 18 carbon atoms; and

R³ is hydroxy, alkoxy of up to about 4 carbon atoms, carboxyl or alkoxycarbonyl of 2 to about 10 carbon atoms.

14. Process according to claim 11 wherein the extraction solution comprises methanol, water and about 10 to 1400 ppm of an alkali metal salt of a carboxylic acid having about 8 to 12 carbon atoms and the aldehyde has the general formula ##STR9## wherein R⁴ is straight- or branched-chain alkylene having about 5 to 20 carbon atoms.

15. Process according to claim 11 wherein the aldehyde has the general formula ##STR10## wherein R⁵ is cycloalkylene having about 5 to 12 carbon atoms;

and

R⁶ is formyl, formylethyl, carboxyl or alkoxycarbonyl of 2 to about 10 carbon atoms.

16. Process for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) a high-boiling aldehyde, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from the group consisting of alkanes having about 5 to 20 carbon atoms, benzene, toluene, xylene isomers, alkyl-substituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, decahydronaphthalene and dialkyl benzenedicarboxylate esters, by the steps of:

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising a primary alkanol and water to form a 2-phase mixture;

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) an alkanol/water phase containing the high-boiling aldehyde;

(3) intimately contacting the alkanol/water phase of step (2) with an organic solvent selected from hydroformylation solvent, olefin feedstock or a mixture thereof; and

(4) separating the mixture of step (3) to obtain;

(a) an organic solvent phase containing catalyst components present in the alkanol/water phase of step (3); and

(b) an alkanol/water phase containing the high-boiling aldehyde.

17. Process according to claim 16 for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) an aldehyde having a boiling point of at least 125°

C., (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from alkanes having about 5 to 20 carbon atoms, alkylsubstituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, and decahydronaphthalene comprising the steps of;

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising methanol and water at a temperature of about 20 to 60°

C. to form a 2-phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) a methanol/water phase containing the aldehyde;

(3) intimately contacting the alkanol/water phase of step (2) with an organic solvent selected from hydroformylation solvent, olefin feedstock or a mixture thereof; and

(4) separating the mixture of step (3) to obtain;

(a) an organic solvent phase containing catalyst components present in the alkanol/water phase of step (3); and

(b) an alkanol/water phase containing the high-boiling aldehyde;

wherein the volume ratio of methanol to water of the extraction solution is about 5;

1 to 1;

1 and the difference between the densities of the hydroformylation product solution and the extraction solution is at least 0.05 g/mL.

18. Process according to claim 17 wherein the process includes (i) heating the methanol/water of step (4)(b) to vaporize at least 50 weight percent of the methanol and form a liquid phase of the aldehyde and

(ii) separating the aldehyde from the liquid phase.

19. Process for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) a high-boiling aldehyde, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from the group consisting of alkanes having about 5 to 20 carbon atoms, benzene, toluene, xylene isomers, alkyl-substituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, decahydronaphthalene and dialkyl benzenedicarboxylate esters, and the conversion of the aldehyde to the corresponding alcohol comprising the steps of:

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising a primary alkanol and water to form a 2-phase mixture; and

(2) separating the mixture of step (1) to obtain;

a hydroformylation solvent phase containing catalyst components; and

(b) an alkanol/water phase containing the high-boiling aldehyde;

(3) subjecting the alkanol/water phase containing the high boiling aldehyde to catalytic hydrogenation to convert the aldehyde to the corresponding alcohol.

20. Process according to claim 19 for the recovery of an aldehyde product from a hydroformylation product solution comprising (i) an aldehyde having a boiling point of at least 125°

C., (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent selected from alkanes having about 5 to 20 carbon atoms, alkyl substituted benzenes having about 9 to 15 carbon atoms, tetrahydronaphthalene, and decahydronaphthalene, and the conversion of the aldehyde to the corresponding alcohol comprising the steps of;

(1) intimately contacting the hydroformylation product solution with an extraction solution comprising methanol and water at a temperature of about 20°

to 60°

C. to form a 2 phase mixture; and

(2) separating the mixture of step (1) to obtain;

(a) a hydroformylation solvent phase containing catalyst components; and

(b) a methanol/water phase containing the aldehyde;

(3) subjecting the methanol/water phase containing the high boiling aldehyde to hydrogenation at a temperature of about 25°

to 150°

C. and a total pressure of about 10 to 1000 psig in the presence of a hydrogenation catalyst;

wherein the volume ratio of methanol to water of the extraction solution is about 5;

1 to 1;

1 and the difference between the densities of the hydroformylation product solution and the extraction solution is at least 0.05 g/mL.

21. Process according to claim 20 wherein the aldehyde has the general formula:

##STR11## wherein R¹ is straight or branched chain alkyl of about 5 to 8 carbon atoms;

R² is straight or branched chain alkylene having about 2 to 18 carbon atoms; and

R³ is hydroxy, alkoxy of up to about 4 carbon atoms, carboxyl or alkoxycarbonyl of 2 to about 10 carbon atoms;

and the hydrogenation is carried out at a temperature of about 100°

to 150°

C. and about 100 to 500 psig in the presence of a catalytic amount of Raney nickel, molybdenum-promoted nickel, Raney cobalt or copper chromite.

22. Process according to claim 20 wherein the aldehyde has the general formula ##STR12## wherein R⁴ is straight or branched chain alkylene having about 5 to 20 carbon atoms;

and the hydrogenation is carried out at a temperature of about 100°

to 150°

C. and about 100 to 500 psig in the presence of a catalytic, amount of Raney nickel, molybdenum promoted nickel, Raney cobalt or copper chromite.

23. Process according to claim 20 wherein the aldehyde has the general formula ##STR13## wherein R⁵ is cycloalkylene having about 5 to 12 carbon atoms;

and

R⁶ is formyl, formylethyl, carboxyl or alkoxycarbonyl of 2 to about 10 carbon atoms; and

the hydrogenation is carried out at a temperature of about 100°

to 150°

C. and about 100 to 500 psig in the presence of a catalytic amount of Raney nickel, molybdenum-promoted nickel, Raney cobalt or copper chromite.