Oxidative conversion of methane to oxygenates

Patent metadata

Field	Value
Publication number	US-10513480-B2
Application number	US-201615774862-A
Country	US
Kind code	B2
Filing date	Nov 9, 2016
Priority date	Nov 10, 2015
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

A method of converting methane to an oxygenate. The method includes converting methane to an oxygenate with a transition metal ion loaded zeolite catalyst in an aqueous medium in the presence of gaseous O2 and CO at a temperature lower than 200° C. Also disclosed are a two-metal ion zeolite catalyst for converting methane to methanol and a method for preparing the two-metal ion zeolite catalyst.

First claim

What is claimed is:

1. A method of converting methane to an oxygenate, the method comprising:
providing a transition metal ion loaded zeolite catalyst,
converting methane to an oxygenate with the transition metal ion loaded zeolite catalyst in an aqueous medium in the presence of gaseous O 2 and CO at a temperature lower than 200° C., and
collecting the oxygenate thus formed,

wherein the transition metal ion loaded zeolite catalyst is a rhodium zeolite catalyst, a copper zeolite catalyst, an iron zeolite catalyst, a nickel zeolite catalyst, an iridium zeolite catalyst, or a combination thereof; and the oxygenate, in liquid form, contains both methanol and acetic acid, in which the content of the methanol, the acetic acid, or both the methanol and the acetic acid combined is greater than 50 mol %.

2. The method of claim 1 , wherein the transition metal ion loaded zeolite catalyst is a rhodium zeolite catalyst.

3. The method of claim 2 , wherein the rhodium zeolite catalyst is a Rh-ZSM-5 or Rh-MOR catalyst.

4. The method of claim 3 , wherein the Rh-ZSM-5 or Rh-MOR catalyst is prepared by incipient wetness impregnation of a rhodium nitrate solution into NH 4 -ZSM-5 or NH 4 -MOR.

5. The method of claim 3 , wherein the Rh-ZSM-5 or Rh-MOR catalyst has a Rh loading of 0.1-1.0 wt %.

6. The method of claim 2 , wherein the rhodium zeolite catalyst is a Rh-ZSM-5 catalyst and the Rh-ZSM-5 catalyst is further treated in 5% H 2 /He at 550° C.

7. The method of claim 2 , wherein the rhodium zeolite catalyst is a Rh-ZSM-5 catalyst and the Rh-ZSM-5 catalyst is prepared from a zeolite having a Si/Al ratio of 15.

8. The method of claim 5 , wherein the Rh-ZSM-5 or Rh-MOR catalyst has a Rh loading of 0.5 wt %.

9. The method of claim 1 , wherein the transition metal ion loaded zeolite catalyst is IrCuPd-ZSM-5 or RhNa-ZSM-5.

10. The method of claim 1 , wherein the transition metal ion loaded zeolite catalyst has a transition metal loading of 0.1-1.0 wt %.

11. A method of converting methane to methanol, the method comprising:
providing a transition metal ion loaded catalyst,
converting methane to methanol with the transition metal ion loaded catalyst in an aqueous medium in the presence of O 2 and CO at a temperature lower than 200° C., and
collecting the methanol thus formed,

wherein the transition metal ion loaded catalyst is a transition metal catalyst loaded on a titanium oxide (TiO 2 ) support or a transition metal zeolite catalyst selected from the group consisting of a rhodium zeolite catalyst, a copper zeolite catalyst, an iron zeolite catalyst, a nickel zeolite catalyst, an iridium zeolite catalyst, and a two-metal ion zeolite catalyst.

12. The method of claim 11 , wherein the transition metal ion loaded catalyst is a rhodium catalyst loaded on a TiO 2 support.

13. The method of claim 11 , wherein the transition metal ion loaded catalyst is a copper zeolite catalyst or an iron zeolite catalyst.

14. The method of claim 11 , wherein the transition metal ion loaded catalyst is a two-metal ion zeolite catalyst.

15. The method of claim 13 , wherein the copper zeolite catalyst or the iron zeolite catalyst has a copper or iron loading of 0.1-1.0 wt %.

16. The method of claim 14 , wherein the two-metal ion zeolite catalyst contains two transition metals selected from the group consisting of Pd and Ir, Cu and Ir, and Fe and Ir.

17. The method of claim 14 , wherein the two-metal ion zeolite catalyst contains two transition metals selected from the group consisting of Pd and Rh, Cu and Rh, and Ag and Rh.

18. The method of claim 16 , wherein the two-metal ion zeolite catalyst has a Pd, Cu, Fe, or Ir loading of 0.1-1.0 wt %.

19. The method of claim 16 , wherein the two transition metals are Cu and Ir, or Fe and Ir.

20. The method of claim 19 , wherein the two-metal ion zeolite catalyst has a Cu, Fe, or Ir loading of 0.1-1.0 wt %, and a Cu/Ir or Fe/Ir molar ratio of 1:1.

21. A two-metal ion zeolite catalyst for converting methane to methanol, the catalyst comprising two transition metals selected from the group consisting of Pd and Ir, Cu and Ir, Fe and Ir, and Pd and Rh.

22. A method of preparing the two-metal ion zeolite catalyst of claim 21 , the method comprising:
forming a transition metal ion loaded zeolite catalyst, the catalyst containing a first transition metal,
introducing a second transition metal into the catalyst thus formed to obtain a two-metal ion zeolite catalyst, and
reducing the two-metal ion zeolite catalyst thus obtained in 5% H 2 /He, wherein the two-metal ion zeolite catalyst contains two transition metals selected from the group consisting of Pd and Ir, Cu and Ir, Fe and Ir, and Pd and Rh.

Assignees

• Tufts College

Inventors

• Shan Junjun
• Flytzani-Stephanopoulos Maria
• Li Mengwei

Classifications

• B01J29/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• B01J29/46

  Iron group metals or copper · CPC title

• B01J23/464

  Rhodium · CPC title

• C07C29/50 Primary

  with molecular oxygen only · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title