Diaminoalkane syntheses via selective amination of hydroxyaldehydes

• US 6,147,261 A
• Filed: 11/17/1999
• Issued: 11/14/2000
• Est. Priority Date: 11/23/1998
• Status: Expired due to Fees

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Janitor, Daniel John, Knifton, John Frederik
• Primary Examiner(s): Richter, Johann
• Assistant Examiner(s): Davis, Brian J.
• Application Number:
  US09/442,234
• Time in Patent Office: 363 Days
• Field of Search: 564/471, 564/473
• US Class Current: 564/473
• CPC Class Codes: C07C 209/16 with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
• CPC Class Codes: C07C 209/22 by substitution of other functional groups
• CPC Class Codes: C07C 211/11 Diaminopropanes

Abstract

Disclosed is a process for producing diaminoalkanes which comprises reacting a hydroxyalkanal characterized by two to six carbons, preferably 3-hydroxypropanal, with excess ammonia and sufficient hydrogen to stabilize a nickel or cobalt-containing hydroamination catalyst, at a temperature of at least 50° C. and a pressure of at least 500 psig, until there is substantial formation of the desired diaminoalkane, wherein said catalyst comprises at least one metal selected from the group consisting of nickel and cobalt, or mixtures thereof, optionally in the presence of one or more promoters.

Claims

1. A process for the production of diaminoalkanes which comprises:

introducing into a reactor one or more by hydroxyalkanals;

reacting said hydroxyalkanal in the presence of excess ammonia and hydrogen and in the presence of a catalyst comprising at least one metal selected from nickel or cobalt, or a mixture thereof, optionally on a support or as a bulk-metal catalyst;

reacting said hydroxyalkanal at a temperature of from 140°

C. to 180°

C. at a pressure of at least 500 psi; and

separating the diaminoalkane product.

2. The process of claim 1 wherein the hydroxyalkanal is 3-hydroxypropanal and the product dialkylamine is 1,3-diaminopropane.

3. The process of claim 2 wherein the pressure is from 500 psi to 5000 psi.

4. The process of claim 3 wherein the pressure is from 1000 psi to 3000 psi.

5. The process of claim 2 further comprising introducing the 3-hydroxypropanal into the reactor in a solvent selected from the group consisting of methyl tertiary-butyl ether, tertiary-butanol, and water.

6. The process of claim 5 wherein the solvent is water.

7. The process of claim 2 wherein the molar ratio of ammonia to hydroxyalkanal is 5 to 200:

1.

8. The process of claim 2 wherein the hydrogen is fed to the reactor at a rate of 0.1-100 mole hydrogen/mole 3-hydroxypropanal.

9. The process of claim 1 wherein the catalyst contains on an oxide-free basis about 10-80% cobalt.

10. The process of claim 9 wherein the catalyst further comprises from about 10 to 80% cobalt, plus a nickel and molybdenum promoter.

11. The process of claim 1 wherein the catalyst comprises on an oxide-free basis from about 10 to 80 wt % nickel, plus a molybdenum promoter.

12. The process of claim 9 further comprising the use of one or more promoters selected from the group consisting of Group IB and Group VIB of the Periodic Table.

13. The process of claim 12 wherein the promoters are selected from the group consisting of tungsten, copper, molybdenum, and chromium.

14. The process of claim 9 wherein the catalyst comprises on an oxide-free basis from about 50 to 60% cobalt.

15. The process of claim 1 wherein the catalyst comprises at least one metal selected from the group consisting of nickel and cobalt on a support.

16. The process of claim 15 wherein the support is selected from Groups IIa, IIIa, IVa, or Va of the Periodic Table.

17. The process of claim 15 wherein the support is selected from the group consisting of magnesia, alumina, silica, zirconia, and titania, as well as mixtures thereof.

24. The process of claim 1 wherein the nickel catalyst is a bulk-metal nickel catalyst.

25. The process of claim 24 wherein the nickel catalyst contains about 10-80% nickel.

26. The process of claim 24 wherein the bulk-metal nickel catalyst also contains molybdenum oxide.

27. The process of claim 24 wherein the bulk-metal nickel catalyst also contains copper and chromium.

18. A two-step process for the production of 1,3-diaminopropane which comprises:

a) introducing into a reactor 3-hydroxypropanal, reacting said 3-hydroxypropanal in the presence of excess ammonia and hydrogen and in the presence of a nickel catalyst at a temperature of at least 50°

C. and a pressure of at least 500 psi;

generating an intermediate comprising 3-amino-1-propanol,

b) reacting said 3-amino-1-propanol in the presence of excess ammonia and hydrogen and in the presence of a cobalt catalyst, at a temperature of 140 to 200°

C. and a pressure of 1000 to 3000 psi; and

isolating said 1,3-diaminopropane.

19. The process of claim 18 wherein the temperature in the first step is 100-150°

C.

20. The process of claim 18 wherein the pressure in step a) is from 500 psi to 5000 psi.

21. The process of claim 18 further comprising introducing the 3-hydroxypropanal into the reactor in a solvent comprising water.

22. The process of claim 18 wherein the molar ratio of ammonia to 3-hydroxypropanal is 5-200:

1.

23. The process of claim 18 wherein the hydrogen is fed to the reactor at a rate of 0.1-100 mole hydrogen/mole 3-hydroxypropanal.