Sulfur as a selective oxidant in oxidative hydrocarbon processing over oxide/chalcogenide catalysts

Patent metadata

Field	Value
Publication number	US-10227268-B2
Application number	US-201615513494-A
Country	US
Kind code	B2
Filing date	Feb 19, 2016
Priority date	Feb 19, 2015
Publication date	Mar 12, 2019
Grant date	Mar 12, 2019

Abstract

Methods for oxidative coupling of methane using metal oxide catalysts and a sulfur oxidant.

First claim

We claim:

1. A method for oxidatively coupling methane, said method comprising:
providing a metal oxide component;
exposing said metal oxide component to gaseous S 2 in the absence of methane for a time and at a temperature sufficient for at least partial sulfidation of said metal oxide component to produce an at least partially sulfidated metal oxide component; and
contacting said at least partially sulfidated metal oxide component with methane at a methane flow rate and for a time sufficient to oxidatively couple said methane and produce ethylene.

2. The method of claim 1 wherein said metal oxide component is selected from the group consisting of MgO, ZrO 2 , TiO 2 , CeO 2 , Sm 2 O 3 , ZnO, WO 3 , Cr 2 O 3 , La 2 O 3 , and Fe 3 O 4 .

3. The method of claim 1 wherein each of said gaseous S 2 and methane is carried with Ar.

4. The method of claim 1 wherein H 2 S is contacted with said at least partially sulfidated metal oxide component.

5. The method of claim 1 wherein ethylene is selectively produced over ethane and acetylene.

6. A method for oxidatively coupling methane, said method comprising:
providing a metal oxide component selected from the group consisting of MgO, ZrO 2 , TiO 2 , CeO 2 , Sm 2 O 3 , ZnO, WO 3 , Cr 2 O 3 , La 2 O 3 , and Fe 3 O 4 ;
exposing said metal oxide component to gaseous S 2 in the absence of methane for a time and at a temperature sufficient for at least partial sulfidation of said metal oxide component to produce an at least partially sulfidated metal oxide component; and
contacting said at least partially sulfidated metal oxide component with methane at a methane flow rate and for a time sufficient to oxidatively couple said methane and selectively produce ethylene over ethane and acetylene.

7. The method of claim 6 wherein each of said gaseous S 2 and methane is carried with Ar.

8. The method of claim 6 wherein H 2 S is contacted with said at least partially sulfidated metal oxide component.

9. The method of claim 6 wherein coke deposits are formed on said at least partially sulfidated metal oxide component during said contacting said at least partially sulfidated metal oxide component with methane.

10. The method of claim 6 wherein said oxidative coupling of methane further produces ethane and wherein increasing said contact time increases the ethylene/ethane molar ratio.

11. A method of using a metal oxide catalyst to oxidatively couple methane, said method comprising:
providing a metal oxide catalyst component absent the presence of a noble metal;
exposing said metal oxide catalyst component to gaseous S 2 in the absence of methane for a time and at a temperature sufficient for at least partial sulfidation of said metal oxide catalyst component to produce an at least partially sulfidated metal oxide catalyst component; and
contacting said at least partially sulfidated metal oxide catalyst component with methane at a methane flow rate and for a time sufficient to oxidatively couple said methane and produce ethylene.

12. The method of claim 11 wherein each of said gaseous S 2 and methane is carried with Ar.

13. The method of claim 11 wherein H 2 S is contacted with said at least partially sulfidated metal oxide catalyst component.

14. The method of claim 11 wherein coke deposits are formed on said at least partially sulfidated metal oxide catalyst component during said contacting said at least partially sulfidated metal oxide catalyst component with methane.

15. The method of claim 11 wherein said oxidative coupling of methane further produces ethane and wherein increasing said contact time increases the ethylene/ethane molar ratio.

16. The method of claim 11 wherein said metal oxide catalyst component is selected from the group consisting of MgO, ZrO 2 , TiO 2 , CeO 2 , Sm 2 O 3 , ZnO, WO 3 , Cr 2 O 3 , La 2 O 3 , and Fe 3 O 4 .

17. The method of claim 15 wherein said metal oxide catalyst component is a particulate with a diameter of about 180 μm to about 300 μm.

18. A method for oxidatively coupling methane, said method comprising:
providing a metal oxide component selected from the group consisting of TiO 2 , CeO 2 , ZnO, WO 3 , Cr 2 O 3 , La 2 O 3 , and Fe 3 O 4 ;
exposing said metal oxide component to gaseous S 2 for a time and at a temperature sufficient for at least partial sulfidation of said metal oxide component to produce an at least partially sulfidated metal oxide component; and
contacting said at least partially sulfidated metal oxide component with methane at a methane flow rate and for a time sufficient to oxidatively couple said methane and produce ethylene.

19. The method of claim 18 , wherein the metal oxide component is Fe 3 O 4 .

20. The method of claim 18 , wherein the metal oxide component is CeO 2 .

Assignees

• Univ Northwestern

Inventors

• Marks Tobin J
• Peter Matthias

Classifications

• Y02P20/52

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

• B01J23/24

  Chromium, molybdenum or tungsten · CPC title

• B01J27/04

  Sulfides · CPC title

• B01J35/1014

  Operations & Transport · mapped topic

• B01J37/20

  Sulfiding · CPC title