IP Library › Granted Patent US 9,446,387
Granted Patent B2
US 9,446,387 · App. 14/692,495 · Granted Sep 20, 2016

Catalysts for petrochemical catalysis

Inventors: Joel M. Cizeron (Redwood City, CA); Erik C. Scher (San Francisco, CA); Fabio R. Zurcher (Brisbane, CA); Wayne P. Schammel (Brisbane, CA); Greg Nyce (Pleasanton, CA); Anja Rumplecker (San Francisco, CA); Jarod McCormick (San Carlos, CA); Marian Alcid (Sunnyvale, CA); Joel Gamoras (Vallejo, CA); Daniel Rosenberg (San Francisco, CA); Erik-Jan Ras (Amsterdam, NL)
Assignee: Siluria Technologies, Inc.
B01J23/8892B01J19/0046B01J21/066B01J21/08B01J23/002B01J23/10B01J23/34B01J23/54B01J23/63B01J23/76B01J23/83B01J27/16B01J35/0006B01J37/031B01J37/035C07C2/84B01J2219/00527B01J2219/00536B01J2219/00702B01J2219/00747B01J2523/00C07C2521/10C07C2521/14C07C2523/10C07C2523/34C07C2529/072C07C2529/076C07C2529/89Y02P20/52
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Quick Facts
Patent No.
US 9,446,387
App. No.
14/692,495
Granted
Sep 20, 2016
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 (54)

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 one of 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 10% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 700° 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, 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. The catalyst of claim 1 , wherein the oxidative coupling of methane is performed at total reaction pressures ranging from 1 atm to 10 atm.

21. The catalyst of claim 1 , 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.

22. The catalyst of claim 1 , 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.

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

24. A catalytic material comprising the catalyst of claim 1 in combination with a support material.

25. The catalytic material of claim 24 , 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.

26. A catalyst comprising a rare earth metal oxyhydroxide, rare earth metal oxyhalide, rare earth metal oxynitrate or rare earth metal phosphate, the catalyst further comprising at least one doping element from one of groups 1-16, lanthanides, actinides or combinations thereof, and wherein the catalyst comprises a C2 selectivity of greater than 50% and a methane conversion of greater than 10% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 700 ° C. or less.

27. The catalyst of claim 26 , wherein the at least one doping element is selected from groups 1-4, 8, 13, 14, lanthanides, actinides and combinations thereof.

28. The catalyst of claim 26 , wherein the at least one doping element is selected from groups 1-6, 8, 11, 13-15, lanthanides, actinides and combinations thereof.

29. The catalyst of claim 26 , wherein the at least one doping element is a rare earth element.

30. The catalyst of claim 26 , 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.

31. The catalyst of claim 26 , wherein the catalyst comprises a combination of at least two different doping elements.

32. The catalyst of claim 31 , 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.

33. The catalyst of claim 31 , 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, 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.

34. The catalyst of claim 26 , wherein the catalyst comprises a combination of at least three different doping elements.

35. The catalyst of claim 34 , 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.

36. The catalyst of claim 26 , wherein the catalyst comprises a combination of at least four different doping elements.

37. The catalyst of claim 36 , 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.

38. The catalyst of claim 26 , wherein the catalyst comprises a lanthanum oxyhydroxide, a lanthanum oxyhalide, a lanthanum oxynitrate or a lanthanum phosphate.

39. The catalyst of claim 26 , wherein the catalyst comprises a neodymium oxyhydroxide, a neodymium oxyhalide, a neodymium oxynitrate or a neodymium phosphate.

40. The catalyst of claim 26 , wherein the catalyst comprises a ytterbium oxyhydroxide, a ytterbium oxyhalide, a ytterbium oxynitrate or a ytterbium phosphate.

41. The catalyst of claim 26 , wherein the catalyst comprises a europium oxyhydroxide, a europium oxyhalide, a europium oxynitrate or a europium phosphate.

42. The catalyst of claim 26 , wherein the catalyst comprises a samarium oxyhydroxide, a samarium oxyhalide, a samarium oxynitrate or a samarium phosphate.

43. The catalyst of claim 26 , wherein the catalyst comprises a yttrium oxyhydroxide, a yttrium oxyhalide, a yttrium oxynitrate or a yttrium phosphate.

44. The catalyst of claim 26 , wherein the catalyst comprises a cerium oxyhydroxide, a cerium oxyhalide, a cerium oxynitrate or a cerium phosphate.

45. The catalyst of claim 26 , wherein the catalyst comprises a praseodymium oxyhydroxide, a praseodymium oxyhalide, a praseodymium oxynitrate or a praseodymium phosphate.

46. The catalyst of claim 26 , wherein the oxidative coupling of methane is performed at total reaction pressures ranging from 1 atm to 10 atm.

47. The catalyst of claim 26 , 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.

48. The catalyst of claim 26 , 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.

49. The catalyst of claim 26 , wherein the oxidative coupling of methane is performed at a temperature of 700° C. or less.

50. A catalytic material comprising the catalyst of claim 26 in combination with a support material.

51. The catalytic material of claim 50 , 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.

Continuity (5)
Continuation 14517524 · Oct 17, 2014
Continuation 13479767 · May 24, 2012
Provisional Application 61564832 · Nov 29, 2011
Provisional Application 61489651 · May 24, 2011
Related Publication 20150224482A1 · Aug 13, 2015