Process for the manufacture of propylene oxide

• US 8,735,613 B2
• Filed: 11/24/2010
• Issued: 05/27/2014
• Est. Priority Date: 11/27/2009
• Status: Active Grant

• Current Assignee: Evonik Degussa GmbH
• Original Assignee: Momentive Specialty Chemicals Incorporated (Momentive Performance Materials Holdings LLC)
• Inventors: Muppa, Prasad, Schoolderman, Caspar, Rens Van Der Lee, Sandra, Postma, Ron
• Primary Examiner(s): OH, TAYLOR V
• Application Number:
  US13/512,167
• Publication Number:
  US 20120289722A1
• Time in Patent Office: 1,280 Days
• Field of Search: 549/531
• US Class Current: 549/531
• CPC Class Codes: C07D 301/12 with hydrogen peroxide or inorganic peroxides or peracids
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A process for the manufacture of propylene oxide (“PO”) by catalytic oxidation of propylene with an oxidant wherein the catalytic oxidation is performed in an aqueous reaction medium, comprising water with less than 10% by volume of cosolvents, wherein a water-soluble manganese complex is used as oxidation catalyst,

characterized in that the water-soluble manganese complex is a mononuclear species of the general formula (I):
[LMnX₃]Y   (I)
or a binuclear species of the general formula (II):
[LMn(μ-X)₃MnL]Y₂   (II)
wherein Mn is a manganese; L or each L independently is a polydentate ligand, each X independently is a coordinating species and each μ-X independently is a bridging coordinating species, whereas Y is an non-coordinating counterion, and wherein the catalytic oxidation is carried out at a pH in the range of from 1.5 to 6.0.

Claims

1. A process for the manufacture of propylene oxide, comprising reacting propylene with an oxidant in the presence of a catalyst, in an aqueous reaction medium, comprising water with less than 10% by volume of cosolvents, wherein the catalyst comprises a water-soluble manganese complex which is a mononuclear species of the formula (I):

[LMnX₃]Y (I)

or a binuclear species of the formula (II);

[LMn(μ

-X)₃MnL]Y₂ (II)

wherein Mn is a manganese;

L or each L independently is a polydentate ligand, each X independently is a coordinating species and each μ

-X independently is a bridging coordinating species, and Y is an non-coordinating counterion, and wherein the oxidation is carried out at a pH in the range of from 1.5 to 6.0, and wherein the molar ratio of propylene to the oxidant is from 10;

1 to 1;

1.

2. The process of claim 1 wherein the catalyst comprises a mononuclear manganese complex of the formula (I):

[LMnX₃]Y (I)

or a binuclear manganese complex of the formula (II);

[LMn(μ

-X)₃MnL]Y₂ (II)

wherein Mn is a manganese;

L or each L independently is a polydentate ligand;

each X independently is a coordinating species and each μ

-X independently is a bridging coordinating species, selected from the group consisting of;

RO⁻

, Cl⁻

, Br⁻

, I⁻

, F⁻

, NCS⁻

, N₃⁻

, I₃⁻

, NH₃, NR₃, RCOO⁻

, RSO₃⁻

, RSO₄⁻

, OH⁻

, O²⁻

, O₂²⁻

, HOO⁻

, H₂O, SH⁻

, CN⁻

, OCN⁻

, and S₄²⁻

and combinations thereof, wherein R is a C₁—

C₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is an non-coordinating counterion.

3. The process of claim 2, wherein each polydentate ligand is independently selected from acyclic compounds having at least 7 atoms in the backbone or cyclic compounds having at least 9 atoms in the ring, each having the nitrogen atoms separated by at least two carbon atoms.

4. The process of claim 1, wherein a binuclear water-soluble manganese complex is used as the catalyst.

5. The process of claim 1, wherein the catalyst is used in a molar ratio of the catalyst (Mn) to the oxidant from 1:

100 to 1;

10,000,000.

6. The process of claim 1, wherein the aqueous reaction medium is a water phase.

7. The process of anyone claim 1, wherein the aqueous reaction medium further comprises a buffer system.

8. The process of claim 1, wherein the reaction is carried out at a temperature of from about 5°

C. to about 40°

C. and at pressures from about 0.9 to about 9 bar.

9. The process of claim 1, wherein the oxidant comprises hydrogen peroxide.

10. The process of claim 1, wherein the reaction medium is an aqueous phase and the propylene is a dispersed gas phase dissolved in a liquid phase.

11. The process of claim 1, wherein the reaction medium is a liquid phase and the propylene is present as a dispersed gas phase and a portion of the prolylene oxide leaves the reaction medium as a gas along with unreacted propylene.

12. The process of claim 1, wherein the reaction medium is an aqueous phase and the propylene can also be present as a separate liquid phase.

13. The process of claim 1, wherein the reaction medium is an aqueous phase and the propylene and the propylene oxide are present as a separate liquid phase.

14. The process of claim 1, wherein the oxidant is added to the aqueous reaction medium at a rate about equal to the reaction rate of the oxidation.

15. The process of claim 1, wherein the oxidation is performed in a batch process, in a continuous process or in a semi-continuous process.

16. The process of claim 1, wherein the oxidant comprises hydrogen peroxide, and the ratio of propylene to the hydrogen peroxide is from about 10:

1 to about 1;

1.

17. The process of claim 1, wherein the aqueous reaction medium comprises a 100% aqueous medium excluding any dissolved epoxide and terminal olefin.

18. The process of claim 1, wherein the aqueous reaction medium further comprises a pH in the range of from 2 to 5.

19. The process of claim 1, wherein the buffer system comprises an acid-salt combination.

20. The process of claim 19, wherein the acid-salt combination comprises oxalic acid-oxalate salt.