Electrochemical dehydrogenation, epoxidation, substitution, and halogenation of hydrocarbons and hydrocarbon derivatives

Patent metadata

Field	Value
Publication number	US-12442091-B2
Application number	US-202318334847-A
Country	US
Kind code	B2
Filing date	Jun 14, 2023
Priority date	Dec 8, 2020
Publication date	Oct 14, 2025
Grant date	Oct 14, 2025

Abstract

A method of making alkenes and/or epoxides from alkanes and hydroxy-alkanes, respectively. In a reactor having an anode and a cathode separated by an ion exchange membrane, and containing a solution comprising water, halogen ions, and an alkane and/or a hydroxy-alkane, apply a potential across the anode and the cathode such that a halogenated intermediate is produced at the anode as an anolyte and hydroxyl ions are produced at the cathode as a catholyte; and combining the anolyte and the catholyte to yield an alkene and/or an epoxide.

First claim

What is claimed is:

1. A method of making hydroxy-alkanes and alkenes, the method comprising:
in a reactor comprising an anode and a cathode separated by an ion exchange membrane, and containing a reactant comprising an alkane; and a solution comprising water and halogen ions, and
(a) applying a potential across the anode and the cathode such that halogen radicals are generated from the halogen ions at the anode, the halogen radicals reacting with the alkane to produce a halogenated intermediate as an anolyte, and hydroxyl ions are produced at the cathode as a catholyte; and
(b) combining the anolyte and the catholyte to yield a hydroxy-alkane and/or an alkene;
wherein the solution is substantially free of metal ions that undergo oxidation at the anode under the applied potential.

2. The method of claim 1 , wherein the anode, or the cathode, or both the anode and the cathode are polarizable electrodes.

3. The method of claim 1 , wherein the anode and the cathode comprise a material selected from the group consisting of boron-doped diamond (BDD), tetrahedral amorphous carbon, tetrahedral amorphous carbon nitride, and platinum.

4. The method of claim 1 , wherein the ion exchange membrane is an anion exchange membrane.

5. The method of claim 1 , wherein the alkane comprises a C1-C12-alkane.

6. The method of claim 1 , wherein the alkane comprises a C1-C6-alkane.

7. The method of claim 1 , wherein the halogen ions are selected from the group consisting of chloride ions and bromide ions.

8. The method of claim 7 , wherein the halogen ions are chloride ions.

9. The method of claim 7 , wherein the halogen ions are bromide ions.

10. The method of claim 7 , wherein the method occurs within a temperature range of about 20 to about 100° C.

11. The method of claim 7 , wherein the method occurs within a temperature range of about 20 to about 80° C.

12. The method of claim 1 , wherein the potential applied in step (a) is from about 0.8 V to about 4.0 V vs Ag/AgCl.

13. The method of claim 12 , wherein the potential applied in step (a) is from about 1.8 V to about 2.3 V.

14. The method of claim 1 , wherein the reactant comprises from about 0.001 M alkane to about 5.0 M alkane.

15. The method of claim 1 , wherein the solution comprises from about 0.1 M to about 2.0 M halogen ions.

16. A method of making methanol, the method comprising:
in a reactor comprising an anode and a cathode separated by an ion exchange membrane, and containing a reactant comprising methane, and a solution comprising water and halogen ions;
(a) applying a potential across the anode and the cathode such that halogen radicals are generated from the halogen ions at the anode, the halogen radicals reacting with the methane to produce a halogenated intermediate as an anolyte, and hydroxyl ions are produced at the cathode as a catholyte; and
(b) combining the anolyte and the catholyte to yield methanol;
wherein the solution is substantially free of metal ions that undergo oxidation at the anode under the applied potential.

17. The method of claim 16 , wherein the anode, or the cathode, or both the anode and the cathode are polarizable electrodes.

18. The method of claim 16 , wherein the anode and the cathode comprise a material selected from the group consisting of boron-doped diamond (BDD), tetrahedral amorphous carbon, tetrahedral amorphous carbon nitride, and platinum.

19. The method of claim 16 , wherein the ion exchange membrane is an anion exchange membrane.

Assignees

• Wisconsin Alumni Res Found

Inventors

• Schreier Marcel
• Lucky Christine E

Classifications

• C25B3/25

  Reduction · CPC title

• C25B11/042

  Electrodes formed of a single material · CPC title

• C25B11/043

  Carbon, e.g. diamond or graphene · CPC title

• C25B3/23

  Oxidation (halogenation C25B3/27) · CPC title

• C25B3/03

  Acyclic or carbocyclic hydrocarbons · CPC title