Process for the production of alcohols and diols

• US 5,395,990 A
• Filed: 12/30/1993
• Issued: 03/07/1995
• Est. Priority Date: 12/02/1993
• Status: Expired due to Term

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Scarlett, John
• Primary Examiner(s): LONE, WERREN
• Application Number:
  US08/175,542
• Time in Patent Office: 432 Days
• Field of Search: 568/822, 568/830, 568/864, 568/880, 568/861, 568/862
• US Class Current: 568/864
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/276 with a six-membered ring

Abstract

A process is described for the production of a hydroxylic compound selected from alcohols and diols by hydrogenation of a hydrogenatable material selected from monoesters of carboxylic acids, monoesters of dicarboxylic acids, diesters of dicarboxylic acids, aldehydes, olefinically unsaturated aldehydes, and mixtures of two or more thereof, which process comprises the steps of:

(a) providing a hydrogenation zone containing a charge of a granular hydrogenation catalyst which has a total surface area of at least about 15 m² /g, a pore size distribution such that more than 50% of the pore volume is provided by pores in the size range less than about 40 nm, and a surface area distribution such that more than 50% of the total surface area is provided by pores in the size range of from about 7 nm to about 40 nm;

(b) supplying to the hydrogenation zone a feed stream of a mixture containing hydrogen and the hydrogenatable material;

(c) maintaining the hydrogenation zone under temperature and pressure conditions which are conducive to effecting hydrogenation of the hydrogenatable material; and

(d) recovering from the hydrogenation zone a product stream comprising the hydroxylic compound.

The process is exemplified by the hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to yield 1,4-cyclohexanedimethanol.

Claims

1. A process for the production of alcohols and diols by hydrogenation of a hydrogenatable material selected from C₁ -C₄ alkyl monoesters of C₈ -C₁₈ carboxylic acids, C₁ -C₄ alkyl monoesters of C₄ -C₉ dicarboxylic acids, di-C₁ -C₄ alkyl diesters of C₄ -C₉ dicarboxylic acids, lactones selected from gamma-butyrolactone and epsilon-caprolactone, aldehydes containing up to about 30 carbon atoms, 2-ethyl-hexen-2-al, 2-propylhept-2-enal, 4-methoxycarbonylcyclohexylcarboxaldehyde, and mixtures of two or more thereof, which process comprises the steps of:

(a) providing a hydrogenation zone containing a charge of a granular hydrogenation catalyst which has a total surface area of at least about 15 m² /g, a pore size distribution such that more than 50% of the pore volume is provided by pores in the size range less than about 40 nm, and a surface area distribution such that more than 50% of the total surface area is provided by pores in the size range of from about 7 nm to about 40 nm and wherein the granular hydrogenation catalyst is selected from copper-containing catalysts and Group VIII metal-containing catalysts;

(b) supplying to the hydrogenation zone a feed stream of a mixture containing hydrogen and the hydrogenatable material;

(c) maintaining the hydrogenation zone at a temperature in the range of from about 150°

C. to about 350°

C. and a pressure in the range of from about 150 psia (about 10.34 bar) up to about 2000 psia (about 137.90 bar) to effect hydrogenation of the hydrogenatable material; and

(d) recovering from the hydrogenation zone a product stream comprising the alcohol or diol.

2. A process according to claim 1, in which in step (b) the feed stream is supplied in vaporous form at a feed temperature which is above the dew point of the mixture.

3. A process according to claim 2, in which in step (d) the product stream is recovered in vaporous form at an exit temperature which is above its dew point.

4. A process according to claim 2, in which in step (d) the product stream is recovered as a mixture of liquid and vapour at an exit temperature below the dew point of the stream.

5. A process according to any one of claim 3, in which the hydrogen-containing gas:

hydrogenatable material molar ratio in the vaporous mixture is in the range of from about 200;

1 to about 1000;

1.

6. A process according to claim 5, in which the hydrogenatable material comprises dimethyl 1,4-cyclohexanedicarboxylate.

7. A process according to claim 5, in which the hydrogenatable material comprises a diester selected from di-C₁ -C₄ alkyl esters of a C₄ dicarboxylic acid selected from maleic acid, fumaric acid, succinic acid, and mixtures of two or more thereof.

8. A process according to claim 7, in which the diester comprises dimethyl or diethyl maleate.

9. A process according to claim 5, in which the hydrogenatable material comprises a C₁ -C₄ alkyl monoester of a C₈ to C₁₈ fatty acid.

10. A process according to claim 5, wherein the hydrogenarable material comprises an aldehyde selected from n-butyraldehyde, n-valeraldehyde, 2-ethyl-hexen-2-al, 2-propylhept-2-enal and 4-methoxycarbonylcyclohexylcarboxaldehyde.

11. A process according to claim 5, in which the feed temperature is in the range of from about 200°

C. to about 260°

C. and the feed pressure to the hydrogenation zone is in the range of from about 450 psia (about 3103 bar) to about 1000 psia (about 68.95 bar).

12. A process according to claim 5, in which the catalyst is selected from reduced copper oxide/zinc oxide catalysts, reduced manganese promoted copper catalysts, reduced copper chromite catalysts, reduced promoted copper chromite catalysts, platinum catalysts and palladium catalysts.

13. A process according to claim 12, in which the catalyst is selected from reduced manganese promoted copper catalysts, reduced copper chromite catalysts and reduced promoted copper chromite catalysts.

14. A process according to claim 13, in which the catalyst comprises not more than about 15% by weight of at least one promoter selected from barium, manganese, and mixtures thereof.

15. A process according to claim 12, in which the catalyst is at least partially supported on a supporting material selected from zinc oxide, alumina, silica, silica-alumina, silicon carbide, zirconia, titania, or any combination thereof.

16. A process according to claims 5, in which the hydrogenarable material is supplied at a rate corresponding to a liquid hourly space velocity of from about 0.05 to about 4.0 h^-1.

17. A process according to claim 13, in which the catalyst has a total surface area of at least about 35 m² /g, and at least about 60% of the total surface area of the catalyst is provided by pores in the range of from about 7 to about 40 nm.

18. A process according to claim 17, in which the catalyst has a total surface area of at least about 40 m² /g, and at least about 70% of the total surface area of the catalyst is provided by pores in the range of from about 7 to about 40 nm.

19. A process according to claim 18, in which the catalyst has at least about 70% up to about 85% of its pore volume provided by pores having diameters in the range of from about 7 nm to about 40 nm.

20. A process for the production of cyclohexanedimethanol which comprises the steps of:

(a) providing a hydrogenation zone containing a charge of a granular hydrogenation catalyst which has a total surface area of at least about 40 m² /g, a pore size distribution such that about 70% up to about 85% of the pore volume is provided by pores in the size range of from about 7 nm to about 40 nm, and a surface area distribution such that about 70% up to about 85% of the total surface area is provided by pores in the size range of from about 7 nm to about 40 nm, wherein not more than about 25% of the total surface area is provided by pores in the size range of about 3.7 nm to about 7 nm and wherein the granular hydrogenation catalyst is selected from reduced copper chromite catalysts wherein the Cu;

Cr weight ratio is from about 0.1;

1 to about 4;

1;

reduced, copper chromite catalysts wherein the Cu;

Cr weight ratio is from about 0.1;

1 to about 4;

1 promoted with from about 0.1% by weight up to 15% by weight of barium, manganese or a mixture of barium and manganese;

or reduced manganese promoted copper catalysts wherein the Cu;

Mn weight ratio is from about 2;

1 to about 10;

1;

(b) supplying to the hydrogenation zone a feed stream of a mixture containing hydrogen and di-C₁ -C₄ alkyl cyclohexanedicarboxylate;

(c) maintaining the hydrogenation zone at a temperature of from about 150°

C. to about 350°

C. and a pressure of from about 150 psia (about 10.34 bar) to about 2000 psia (about 137.90 bar); and

(d) recovering from the hydrogenation zone a product stream comprising cyclohexanedimethanol.

21. A process according to claim 20, in which the cyclohexanedimethanol is 1,4-cyclohexanedimethanol, the dialkyl cyclohexanedicarboxylate is dimethyl 1,4-cyclohexanedicarboxylate, the hydrogenation zone is maintained at a temperature of from about 200°

C. to about 260°

C. and a pressure of from about 450 psia (about 31.03 bar) to about 1000 psia (about 68.95 bar).