Oxidation of C1-9-alkanes

Patent metadata

Field	Value
Publication number	US-10479748-B2
Application number	US-201816205521-A
Country	US
Kind code	B2
Filing date	Nov 30, 2018
Priority date	Nov 30, 2017
Publication date	Nov 19, 2019
Grant date	Nov 19, 2019

Abstract

A method for the oxidation of C1-9-alkanes including providing a mixture of a C1-9-alkane in a liquid phase, a boron containing reagent, a free radical initiator, and a drying means, and performing an oxidation reaction at a temperature from 130° C. to 180° C. in the presence of oxygen. The drying means may be a drying agent such as a molecular sieve, or a membrane. Also a composition for oxidation of C1-9-alkanes to sec-C1-9-alcohols.

First claim

Claimed is:

1. A method for oxidation of C 1-9 -alkanes, the method comprising:
providing a mixture of:
a C 1-9 -alkane in a liquid phase;
a boron containing reagent;
a free radical initiator; and
a drying means; and,

performing an oxidation reaction at a temperature from 130° C. to 180° C. in the presence of oxygen.

2. The method of claim 1 wherein the mixture is at a pressure from 2 to 5 MPa.

3. The method of claim 2 wherein the pressure is from 2 to 3 MPa.

4. The method of claim 1 , wherein the boron containing reagent is a borate ester.

5. The method of claim 4 wherein the borate ester is a metaborate ester.

6. The method of claim 1 wherein an amount of boron containing reagent is from 1 to 10 mol % with respect to an amount of alkane.

7. The method of claim 1 wherein the free radical initiator is a peroxide.

8. The method of claim 7 wherein the peroxide is a dialkyl peroxide.

9. The method of claim 8 wherein the dialkyl peroxide is di-tert-butyl peroxide.

10. The method of claim 1 wherein the drying means is a drying agent.

11. The method of claim 10 wherein the drying agent is a molecular sieve.

12. The method of claim 11 wherein the molecular sieves are 3 Å molecular sieves.

13. The method of claim 1 wherein the drying means is a semi-permeable membrane.

14. The method of claim 13 wherein the semi-permeable membrane is a hydrophilic pervaporation membrane.

15. The method of claim 1 wherein the drying means is a combination of a drying agent and a semi-permeable membrane.

16. The method of claim 1 wherein the oxygen comprises a mixture of oxygen and nitrogen gases.

17. The method of claim 16 wherein the mixture of oxygen and nitrogen gases contains from about 1 to 10 vol % oxygen.

18. The method of claim 1 wherein the temperature is between 130° C. and 150° C.

19. The method of claim 18 wherein the mixture is maintained at the temperature between 130° C. and 150° C. for 0.5 to 8 hours.

20. The method of claim 1 wherein the alkane is pentane.

21. The method of claim 20 wherein the pentane is n-pentane.

22. The method of claim 1 further comprising:
a hydrolysis step in which a borate ester produced during the oxidation reaction is treated with water to produce an alcohol.

23. The method of claim 1 further comprising:
a conversion step in which an alcohol produced during the oxidation reaction is converted to an olefin, an ester, an ether or a higher molecular weight product.

24. The method of claim 23 wherein prior to the conversion step, the alcohol is recovered from the oxidation reaction by hydrolysis.

25. The method of claim 1 further comprising:
a conversion step wherein borate ester produced during the oxidation reaction is converted directly to an olefin by thermal decomposition at a temperature of at least 300° C.

26. The method of claim 1 further comprising:
a step of recovering unreacted alkane from the reaction mixture after the oxidation reaction.

27. A composition for oxidation of C 1-9 -alkanes to sec-C 1-9 -alcohols, the composition comprising:
a C 1-9 -alkane in a liquid phase;
a boron containing reagent;
a free radical initiator; and
a drying agent.

Assignees

• Cambridge Entpr Ltd

Inventors

• Lapkin Alexei
• Aworinde Samson
• Wang Kun

Classifications

• C07C29/172 Primary

  with the obtention of a fully saturated alcohol · CPC title

• C07C45/33

  of CHx-moieties · CPC title

• C07C27/12

  with oxygen · CPC title

• C07C49/04

  Saturated compounds containing keto groups bound to acyclic carbon atoms · CPC title

• C07C29/52 Primary

  in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed · CPC title