Production of ethylene with nanowire catalysts

Patent metadata

Field	Value
Publication number	US-9718054-B2
Application number	US-201113115082-A
Country	US
Kind code	B2
Filing date	May 24, 2011
Priority date	May 24, 2010
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

Methods for producing ethylene using nanowires as heterogeneous catalysts are provided. The method includes, for example, an oxidative coupling of methane catalyzed by nanowires to provide ethylene.

First claim

The invention claimed is:

1. A method for the preparation of ethylene from methane, the method comprising contacting a mixture comprising oxygen and methane at a temperature below 600° C. with a catalytic nanowire, thereby producing C2 hydrocarbons at a selectivity of greater than 30%, wherein the catalytic nanowire is an inorganic catalytic polycrystalline nanowire having a ratio of effective length to actual length of less than one and an aspect ratio of greater than ten as measured by TEM in bright field mode at 5 keV, wherein the catalytic nanowire comprises one or more elements from any of Groups 1 through 7, lanthanides, actinides or combinations thereof in the form of oxides, hydroxides, oxyhydroxides, sulfates, carbonates, oxide carbonates, oxalates, phosphates, hydrogenphosphates, dihydrogenphosphates, oxyhalides, hydroxihalides, oxysulfates or combinations thereof.

2. A method for preparing a downstream product of ethylene, the method comprising converting ethylene into a downstream product of ethylene, and the method comprising contacting a mixture comprising oxygen and methane at a temperature below 600° C. with a catalytic nanowire, thereby producing C2 hydrocarbons at a selectivity of greater than 30%, wherein the catalytic nanowire is an inorganic catalytic polycrystalline nanowire having a ratio of effective length to actual length of less than one and an aspect ratio of greater than ten as measured by TEM in bright field mode at 5 keV, wherein the catalytic nanowire comprises one or more elements from any of Groups 1 through 7, lanthanides, actinides or combinations thereof in the form of oxides, hydroxides, oxyhydroxides, sulfates, carbonates, oxide carbonates, oxalates, phosphates, hydrogenphosphates, dihydrogenphosphates, oxyhalides, hydroxihalides, oxysulfates or combinations thereof.

3. A method for the preparation of a downstream product of ethylene, the method comprising:
converting methane into ethylene by contacting a mixture comprising oxygen and methane at a temperature below 600° C. with a catalytic nanowire, thereby producing C2 hydrocarbons at a selectivity of greater than 30%; and
oligomerizing the ethylene to prepare a downstream product of ethylene, wherein the catalytic nanowire is an inorganic catalytic polycrystalline nanowire having a ratio of effective length to actual length of less than one and an aspect ratio of greater than ten as measured by TEM in bright field mode at 5 keV, wherein the catalytic nanowire comprises one or more elements from any of Groups 1 through 7, lanthanides, actinides or combinations thereof in the form of oxides, hydroxides, oxyhydroxides, sulfates, carbonates, oxide carbonates, oxalates, phosphates, hydrogenphosphates, dihydrogenphosphates, oxyhalides, hydroxihalides, oxysulfates or combinations thereof.

4. The method of claim 1 , wherein the one or more elements are in the form of oxides.

5. The method of claim 1 , wherein the one or more elements are in the form of hydroxides.

6. The method of claim 1 , wherein the catalytic nanowire comprises Mg, Ca, La, W, Mn, Mo, Nd, Sm, Eu, Pr, Zr or combinations thereof.

7. The method of claim 1 , wherein the catalytic nanowire comprises MgO, CaO, La 2 O 3 , Na 2 WO 4 , Mn 2 O 3 , Mn 3 O 4 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Pr 2 O 3 , Mg 6 MnO 8 , NaMnO 4 , Na/Mn/W/O, MnWO 4 or combinations thereof.

8. The method of claim 1 , wherein the catalytic nanowire further comprises one or more dopants comprising metal elements, semi-metal elements, non-metal elements or combinations thereof.

9. The method of claim 8 , wherein the dopant comprises Li, Na, K, Mg, Ca, Ba, Sr, Eu, Sm, Co or Mn.

10. The method of claim 9 , wherein the catalytic nanowire comprises Li/MgO, Ba/MgO, Sr/La 2 O 3 , Mg/Na/La 2 O 3 , Sr/Nd 2 O 3 , or Mn/Na 2 WO 4 .

11. The method of claim 8 , wherein the atomic ratio of the one or more elements from Groups 1 through 7, lanthanides or actinides to the dopant ranges from 1:1 to 10,000:1.

12. The method of claim 1 , wherein the catalytic nanowire comprises a combination of two or more compounds comprising the one or more elements.

13. The method of claim 12 , wherein the catalytic nanowire comprises Mn 2 O 3 /Na 2 WO 4 , Mn 3 O 4 /Na 2 WO 4 MnWO 4 /Na 2 WO 4 /Mn 2 O 3 , MnWO 4 /Na 2 WO 4 /Mn 3 O 4 or NaMnO 4 /MgO.

14. The method of claim 1 , wherein the catalytic nanowire has a diameter of between 7 nm and 200 nm as determined by TEM in bright field mode at 5 keV.

15. The method of claim 1 , wherein the catalytic nanowire has an actual length of between 100 nm and 10 μm as determined by TEM in bright field mode at 5 keV.

16. The method of claim 1 , wherein the catalytic nanowire has a ratio of effective length to actual length of less than 0.8.

17. The method of claim 1 , wherein the powder x-ray diffraction pattern of the nanowire shows an average crystalline domain size of less than 50 nm.

18. The method of claim 1 , wherein the catalytic nanowire further comprises a support material.

19. The method of claim 18 , wherein the support material comprises an inorganic oxide, Al 2 O 3 , SiO 2 , TiO 2 , MgO, ZrO 2 , HfO 2 , CaO, ZnO, LiAlO 2 , MgAl 2 O 4 , MnO, MnO 2 , Mn 2 O 4 , Mn 3 O 4 , La 2 O 3 , activated carbon, silica gel, zeolites, activated clays, activated Al 2 O 3 , diatomaceous earth, magnesia, aluminosilicates, calcium aluminate, support nanowires or combinations thereof.

20. The method of claim 1 , wherein the catalytic nanowire comprises an inner core and an outer layer, the inner core and outer layer each independently comprising one or more elements selected from Groups 1 through 7, lanthanides and actinides.

21. The method of claim 1 , wherein the ethylene is prepared from methane via the oxidative coupling of methane (OCM) reaction.

22. The method of claim 1 , wherein the mixture comprising oxygen and methane comprises air.

23. The method of claim 2 , wherein the one or more elements are in the form of oxides.

24. The method of claim 2 , wherein the one or more elements are in the form of hydroxides.

25. The method of claim 2 , wherein the catalytic nanowire comprises Mg, Ca, La, W, Mn, Mo, Nd, Sm, Eu, Pr, Zr or combinations thereof.

26. The method of claim 2 , wherein the catalytic nanowire comprises MgO, CaO, La 2 O 3 , Na 2 WO 4 , Mn 2 O 3 , Mn 3 O 4 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Pr 2 O 3 , Mg 6 MnO 8 , NaMnO 4 , Na/Mn/W/O, MnWO 4 or combinations thereof.

27. The method of claim 2 , wherein the catalytic nanowire further comprises one or more dopants comprising metal elements, semi-metal elements, non-metal elements or combinations thereof.

28. The method of claim 27 , wherein the dopant comprises Li, Na, K, Mg, Ca, Ba, Sr, Eu, Sm, Co or Mn.

29. The method of claim 28 , wherein the catalytic nanowire comprises Li/MgO, Ba/MgO, Sr/La 2 O 3 , Mg/Na/La 2 O 3 , Sr/Nd 2 O 3 , or Mn/Na 2 WO 4 .

30. The method of claim 27 , wherein the atomic ratio of the one or more elements from Groups 1 through 7, lanthanides or actinides to the dopant ranges from 1:1 to 10,000:1.

31. The method of claim 2 , wherein the catalytic nanowire comprises a combination of two or more compounds comprising the one or more elements.

32. The method of claim 31 , wherein the catalytic nanowire comprises Mn 2 O 3 /Na 2 WO 4 , Mn 3 O 4 /Na 2 WO 4 MnWO 4 /Na 2 WO 4 /Mn 2 O 3 , MnWO 4 /

Assignees

• Scher Erik C
• Zurcher Fabio R
• Cizeron Joel M
• Schammel Wayne P
• Tkachenko Alex
• Gamoras Joel
• Karshtedt Dmitry
• Nyce Greg
• Siluria Technologies Inc

Inventors

• Scher Erik C
• Zurcher Fabio R
• Cizeron Joel M
• Schammel Wayne P
• Tkachenko Alex
• Gamoras Joel
• Karshtedt Dmitry
• Nyce Greg

Classifications

• C07C2523/75

  Cobalt · CPC title

• B01J21/066

  Zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• C07C2523/30

  Tungsten · CPC title

• B01J23/22

  Vanadium · CPC title

• C01G25/00

  Compounds of zirconium · CPC title