Nanowire catalysts and methods for their use and preparation

Patent metadata

Field	Value
Publication number	US-9751818-B2
Application number	US-201414557225-A
Country	US
Kind code	B2
Filing date	Dec 1, 2014
Priority date	Nov 29, 2011
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

Abstract

Nanowires useful as heterogeneous catalysts are provided. The nanowire catalysts are useful in a variety of catalytic reactions, for example, the oxidative coupling of methane to C2 hydrocarbons. Related methods for use and manufacture of the same are also disclosed.

First claim

The invention claimed is:

1. A method for the preparation of ethane, ethylene or combinations thereof, the method comprising contacting a catalytic material with a gas comprising methane, wherein the catalytic material is in the form of a pressed pellet, extrudate or monolith and comprises:
a) a plurality of catalytic nanowires, the catalytic nanowires comprising one or more doping elements; and
b) a diluent or support selected from one or more alkaline earth metal compounds,
and wherein the catalytic material has a C2+ yield above 5% when employed as catalytic material in the oxidative coupling of methane at an inlet temperature of 550° C. and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000/hr.

2. The method of claim 1 , wherein the catalytic materials is in the form of a pressure treated, pressed pellet and comprises no binder material.

3. The method of claim 1 , wherein the catalytic material is in the form of a pressed pellet or extrudate and comprises pores greater than 20 nm in diameter.

4. The method of claim 1 , wherein the alkaline earth metal compound is an alkaline earth metal oxide, alkaline earth metal carbonate, alkaline earth metal sulfate or alkaline earth metal phosphate.

5. The method of claim 1 , wherein the alkaline earth metal compound is an alkaline earth metal carbonate, alkaline earth metal sulfate or alkaline earth metal phosphate.

6. The method of claim 1 , wherein the alkaline earth metal compound is MgO, MgCO 3 , MgSO 4 , Mg 3 (PO 4 ) 2 , MgAl 2 O 4 , CaO, CaCO 3 , CaSO 4 , Ca 3 (PO 4 ) 2 , CaAl 2 O 4 , SrO, SrCO 3 , SrSO 4 , Sr 3 (PO 4 ) 2 , SrAl 2 O 4 , BaO, BaCO 3 , BaSO 4 , Ba 3 (PO 4 ) 2 , BaAl 2 O 4 or combinations thereof.

7. The method of claim 1 , wherein the alkaline earth metal compound is MgCO 3 , MgSO 4 , Mg 3 (PO 4 ) 2 , CaO, CaCO 3 , CaSO 4 , Ca 3 (PO 4 ) 2 , CaAl 2 O 4 , SrO, SrCO 3 , SrSO 4 , Sr 3 (PO 4 ) 2 , SrAl 2 O 4 , BaO, BaCO 3 , BaSO 4 , Ba 3 (PO 4 ) 2 , BaAl 2 O 4 or combinations thereof.

8. The method of claim 1 , wherein the alkaline earth metal compound is CaO, SrO, MgCO 3 , CaCO 3 , SrCO 3 or combinations thereof.

9. The method of claim 1 , wherein the plurality of catalytic nanowires have a ratio of average effective length to average actual length of less than one and an average aspect ratio of greater than ten as measured by TEM in bright field mode at 5 keV, wherein the plurality of catalytic nanowires comprises one or more elements from any of Groups 1 through 7, lanthanides, actinides or combinations thereof.

10. The method of claim 1 , wherein the plurality of catalytic nanowires comprises straight nanowires.

11. The method of claim 10 , wherein the straight nanowires have a ratio of effective length to actual length equal to one.

12. The method of claim 1 , wherein the plurality of catalytic nanowires comprises at least one nanowire selected from any one of Tables 1-12.

13. The method of claim 1 , wherein the catalytic material has a C2 selectivity above 50% when employed as catalytic material in the oxidative coupling of methane at an inlet temperature of 550° C. and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000/hr.

14. The method of claim 1 , wherein the catalytic material has a CH 4 conversion above 20% when employed as catalytic material in the oxidative coupling of methane at an inlet temperature of 550° C. and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000/hr.

15. The method of claim 1 , wherein the catalytic material further comprises SiC or cordierite or combinations thereof.

16. The method of claim 1 , wherein the catalytic material is contacted with the gas at a temperature less than 800° C.

17. The method of claim 1 , wherein the catalytic material is contacted with the gas at a temperature less than 700° C.

18. The method of claim 1 , having a conversion of methane to ethylene of greater than 10%.

19. The method of claim 1 , having a yield of ethylene of greater than 10%.

20. The method of claim 1 , having a conversion of methane of greater than 10%.

21. The method of claim 1 , having a C2 yield of greater than 10%.

22. The method of claim 2 , wherein the plurality of catalytic nanowires have a ratio of average effective length to average actual length of less than one and an average aspect ratio of greater than ten as measured by TEM in bright field mode at 5 keV, wherein the plurality of catalytic nanowires comprises one or more elements from any of Groups 1 through 7, lanthanides, actinides or combinations thereof.

23. The method of claim 2 , wherein the plurality of catalytic nanowires comprises straight nanowires.

24. The method of claim 23 , wherein the straight nanowires have a ratio of effective length to actual length equal to one.

25. The method of claim 2 , wherein the plurality of catalytic nanowires comprises at least one nanowire selected from any one of Tables 1-12.

26. The method of claim 2 , wherein the alkaline earth metal compound is an alkaline earth metal oxide, alkaline earth metal carbonate, alkaline earth metal sulfate or alkaline earth metal phosphate.

27. The method of claim 2 , wherein the alkaline earth metal compound is MgO, MgCO 3 , MgSO 4 , Mg 3 (PO 4 ) 2 , MgAl 2 O 4 , CaO, CaCO 3 , CaSO 4 , Ca 3 (PO 4 ) 2 , CaAl 2 O 4 , SrO, SrCO 3 , SrSO 4 , Sr 3 (PO 4 ) 2 , SrAl 2 O 4 , BaO, BaCO 3 , BaSO 4 , Ba 3 (PO 4 ) 2 , BaAl 2 O 4 or combinations thereof.

28. The method of claim 2 , wherein the alkaline earth metal compound is MgO, CaO, SrO, MgCO 3 , CaCO 3 , SrCO 3 or combinations thereof.

29. The method of claim 2 , wherein the catalytic material has a C2 selectivity above 50% when employed as catalytic material in the oxidative coupling of methane at an inlet temperature of 550° C. and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000/hr.

30. The method of claim 2 , wherein the catalytic material has a CH 4 conversion above 20% when employed as catalytic material in the oxidative coupling of methane at an inlet temperature of 550° C. and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000/hr.

31. The method of claim 2 , wherein the catalytic material further comprises SiC or cordierite or combinations thereof.

32. The method of claim 3 , wherein the plurality of catalytic nanowires have a ratio of average effective length to average actual length of less than one and an average aspect ratio of greater than ten as measured by TEM in bright field mode at 5 keV, wherein the plurality of catalytic nanowires comprises one or more elements from any of Groups 1 through 7, lanthanides, actinides or combinations thereof.

33. The method of claim 3 , wherein the plurality of catalytic nanowires comprises straight nanowires.

34. The method of claim 33 , wherein the straight nanowires have a ratio of effective length to actual length equal to one.

35. The method of claim 3 , wherein the plurality of catalytic nanowires comprises at least one nanowire selected from any one of Tables 1-12

Assignees

• Siluria Technologies Inc

Inventors

• Zurcher Fabio R
• Scher Erik C
• Cizeron Joel M
• Schammel Wayne P
• Tkachenko Alex
• Gamoras Joel
• Karshtedt Dmitry
• Nyce Greg
• Rumplecker Anja
• Mccormick Jarod
• Merzlyak Anna
• Alcid Marian
• Rosenberg Daniel
• Ras Erik-Jan

Classifications

• C01G45/02

  Oxides · CPC title

• C07C2523/10

  of rare earths · CPC title

• C01F5/14

  Magnesium hydroxide · CPC title

• C01P2004/80

  Particles consisting of a mixture of two or more inorganic phases · CPC title

• C01P2004/16

  Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer · CPC title