IP Library › Granted Patent US 8,921,256
Granted Patent B2
US 8,921,256 · App. 13/479,767 · Granted Dec 30, 2014

Catalysts for petrochemical catalysis

Inventors: Joel M. Cizeron (Sunnyvale, CA); Erik Scher (San Francisco, CA); Fabio R. Zurcher (Brisbane, CA); Wayne P. Schammel (San Francisco, CA); Greg Nyce (Pleasanton, CA); Anja Rumplecker (San Francisco, CA); Jarod McCormick (San Francisco, CA); Marian Alcid (San Francisco, CA); Joel Gamoras (Vallejo, CA); Daniel Rosenberg (San Francisco, CA); Erik-Jan Ras (Amsterdam, NL)
Assignee: Siluria Technologies, Inc.
B01J23/10B01J23/002B01J23/34B01J23/54B01J23/76C07C2/84B01J37/031B01J37/035B01J23/8892B01J23/63B01J23/83B01J19/0046B01J2523/00B01J2219/00527B01J2219/00536B01J2219/00702B01J2219/00747C07C2523/10C07C2523/34
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Quick Facts
Patent No.
US 8,921,256
App. No.
13/479,767
Granted
Dec 30, 2014
Kind
B2
Abstract

Metal oxide catalysts comprising various dopants are provided. The catalysts are useful as heterogenous catalysts in a variety of catalytic reactions, for example, the oxidative coupling of methane to C2 hydrocarbons such as ethane and ethylene. Related methods for use and manufacture of the same are also disclosed.

Claims (48)

1. A catalyst comprising an oxide of a rare earth element, the catalyst comprising:

the formula Ln1 4-x Ln2 x O 6 , wherein Ln1 and Ln2 are each independently a different lanthanide element, and x is a number ranging from greater than 0 to less than 4; and

at least one doping element from groups 1-16, lanthanides, actinides or combinations thereof,

wherein the catalyst further comprises a C 2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750° C. or less.

2. The catalyst of claim 1 , wherein the at least one doping element is selected from groups 1-4, 8, 13, 14, lanthanides, actinides and combinations thereof.

3. The catalyst of claim 1 , wherein the at least one doping element is selected from groups 1-6, 8, 11, 13-15, lanthanides, actinides and combinations thereof.

4. The catalyst of claim 1 , wherein the at least one doping element is a rare earth element.

5. The catalyst of claim 1 , wherein the at least one doping element is Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te or Mo.

6. The catalyst of claim 1 , wherein the catalyst comprises a combination of at least two different doping elements.

7. The catalyst of claim 6 , wherein the two different doping elements are selected from Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te and Mo.

8. The catalyst of claim 6 , wherein the combination of at least two different doping elements is La/Nd, La/Sm, La/Ce, La/Sr, Eu/Na, Eu/Gd, Ca/Na, Eu/Sm, Eu/Sr, Mg/Sr, Ce/Mg, Gd/Sm, Sr/W, Sr/Ta, Au/Re, Au/Pb, Bi/Hf, Sr/Sn or Mg/N, Ca/S, Rb/S, Sr/Nd, Eu/Y, Mg/Nd, Sr/Na, Nd/Mg, La/Mg, Yb/S, Mg/Na, Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K, Li/K, Rb/Hf, Ca/Cs, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce, Li/Sr, Cs/Zn, Dy/K, La/Mg, In/Sr, Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy, Mg/K, Zr/K, Li/Cs, Sm/Cs, In/K, Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce, Ba/Ta, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb or Sr/Hf.

9. The catalyst of claim 1 , wherein the catalyst comprises a combination of at least three different doping elements.

10. The catalyst of claim 9 , wherein the three different doping elements are selected from Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te and Mo.

11. The catalyst of claim 1 , wherein the catalyst comprises a combination of at least four different doping elements.

12. The catalyst of claim 11 , wherein the four different doping elements are selected from Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te and Mo.

13. The catalyst of claim 1 , wherein Ln1 or Ln2 is lanthanum.

14. The catalyst of claim 1 , wherein Ln1 or Ln2 is neodymium.

15. The catalyst of claim 1 , wherein Ln1 or Ln2 is ytterbium.

16. The catalyst of claim 1 , wherein Ln1 or Ln2 is europium.

17. The catalyst of claim 1 , wherein Ln1 or Ln2 is samarium.

18. The catalyst of claim 1 , wherein Ln1 or Ln2 is cerium.

19. The catalyst of claim 1 , wherein Ln1 or Ln2 is praseodymium.

20. A catalyst comprising an oxide of a rare earth element, wherein the oxide of a rare earth element is a metal oxyhydroxide, metal oxyhalide, a metal oxynitrate or a metal phosphate, wherein the catalyst further comprises at least one doping element from groups 1-16, lanthanides, actinides or combinations thereof, wherein the catalyst comprises a C2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750° C. or less.

21. The catalyst of claim 20 , wherein the at least one doping element is selected from groups 1-4, 8, 13, 14, lanthanides, actinides and combinations thereof.

22. The catalyst of claim 20 , wherein the at least one doping element is selected from groups 1-6, 8, 11, 13-15, lanthanides, actinides and combinations thereof.

23. The catalyst of claim 20 , wherein the at least one doping element is a rare earth element.

24. The catalyst of claim 20 , wherein the at least one doping element is Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te or Mo.

25. The catalyst of claim 20 , wherein the catalyst comprises a combination of at least two different doping elements.

26. The catalyst of claim 25 , wherein the two different doping elements are selected from Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te and Mo.

27. The catalyst of claim 25 , wherein the combination of at least two different doping elements is La/Nd, La/Sm, La/Ce, La/Sr, Eu/Na, Eu/Gd, Ca/Na, Eu/Sm, Eu/Sr, Mg/Sr, Ce/Mg, Gd/Sm, Sr/W, Sr/Ta, Au/Re, Au/Pb, Bi/Hf, Sr/Sn or Mg/N, Ca/S, Rb/S, Sr/Nd, Eu/Y, Mg/Nd, Sr/Na, Nd/Mg, La/Mg, Yb/S, Mg/Na, Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K, Li/K, Rb/Hf, Ca/Cs, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce, Li/Sr, Cs/Zn, Dy/K, La/Mg, In/Sr, Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy, Mg/K, Zr/K, Li/Cs, Sm/Cs, In/K, Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce, Ba/Ta, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb or Sr/Hf.

28. The catalyst of claim 20 , wherein the catalyst comprises a combination of at least three different doping elements.

29. The catalyst of claim 28 , wherein the three different doping elements are selected from Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te and Mo.

30. The catalyst of claim 20 , wherein the catalyst comprises a combination of at least four different doping elements.

31. The catalyst of claim 30 , wherein the four different doping elements are selected from Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd, Hf, Ho, Tm, W, La, K, Dy, In, Cs, S, Zn, Rb, Ba, Yb, Ni, Lu, Ta, P, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, Re, Fe, Al, Tl, Pr, Co, Rh, Ti, V, Cr, Mn, Ir, As, Li, Tb, Er, Te and Mo.

32. The catalyst of claim 20 , wherein the oxide of a rare earth element is a lanthanum oxyhydroxide, a lanthanum oxyhalide, a lanthanum oxynitrate or a lanthanum phosphate.

33. The catalyst of claim 20 , wherein the oxide of a rare earth element is a neodymium oxyhydroxide, a neodymium oxyhalide, a neodymium oxynitrate or a neodymium phosphate.

34. The catalyst of claim 20 , wherein the oxide of a rare earth element is a ytterbium oxyhydroxide, a ytterbium oxyhalide, a ytterbium oxynitrate or a ytterbium phosphate.

35. The catalyst of claim 20 , wherein the oxide of a rare earth element is a europium oxyhydroxide, a europium oxyhalide, a europium oxynitrate or a europium phosphate.

36. The catalyst of claim 20 , wherein the oxide of a rare earth element is a samarium oxyhydroxide, a samarium oxyhalide, a samarium oxynitrate or a samarium phosphate.

37. The catalyst of claim 20 , wherein the oxide of a rare earth element is a yttrium oxyhydroxide, a yttrium oxyhalide, a yttrium oxynitrate or a yttrium phosphate.

38. The catalyst of claim 20 , wherein the oxide of a rare earth element is a cerium oxyhydroxide, a cerium oxyhalide, a cerium oxynitrate or a cerium phosphate.

39. The catalyst of claim 20 , wherein the oxide of a rare earth element is a praseodymium oxyhydroxide, a praseodymium oxyhalide, a praseodymium oxynitrate or a praseodymium phosphate.

40. The catalyst of claim 1 or claim 20 , wherein the oxidative coupling of methane is performed at total reaction pressures ranging from 1 atm to 10 atm.

41. The catalyst of claim 1 or claim 20 , wherein the C 2 selectivity is greater than 60% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750° C. or less.

42. The catalyst of claim 1 or claim 20 , wherein the C 2 yield is greater than 10% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750° C. or less.

43. The catalyst of claim 1 or claim 20 , wherein the oxidative coupling of methane is performed at a temperature of 700° C. or less.

44. A catalytic material comprising the catalyst of claim 1 or claim 20 in combination with a support material.

45. The catalytic material of claim 44 , wherein the support material comprises AlPO 4 , Al 2 O 3 , SiO 2 —Al 2 O 3 , CaO, TiO 2 , ZrO 2 , MgO, SiO 2 , ZrO 2 , HfO 2 , In 2 O 3 , SiC or combinations thereof.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 9, 2012
From: CIZERON, JOEL M.; SCHER, ERIK C.; ZURCHER, FABIO R.; SCHAMMEL, WAYNE P.; NYCE, GREG; RUMPLECKER, ANJA; MCCORMICK, JAROD; ALCID, MARIAN; GAMORAS, JOEL; ROSENBERG, DANIEL; RAS, ERIK-JAN
To: SILURIA TECHNOLOGIES, INC.
Reel/Frame 029100/0486 →
Continuity (3)
Provisional Application 61564832 · Nov 29, 2011
Provisional Application 61489651 · May 24, 2011
Related Publication 20130023709A1 · Jan 24, 2013