Catalysts for petrochemical catalysis

Patent metadata

Field	Value
Publication number	US-9963402-B2
Application number	US-201615228937-A
Country	US
Kind code	B2
Filing date	Aug 4, 2016
Priority date	May 24, 2011
Publication date	May 8, 2018
Grant date	May 8, 2018

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.

First claim

The invention claimed is:

1. A method for the preparation of ethane, ethylene or combinations thereof, the method comprising contacting a catalyst with a gas comprising methane, 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 method 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 method 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 method of claim 1 , wherein the at least one doping element is a rare earth element.

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

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

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

12. The method 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 method of claim 1 , wherein Ln1 or Ln2 is lanthanum.

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

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

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

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

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

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

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

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

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

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

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

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

26. A method for the preparation of ethane, ethylene or combinations thereof, the method comprising contacting a catalyst with a gas comprising methane, the 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 method 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 method 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 method of claim 26 , wherein the at least one doping element is a rare earth element.

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

32. The method 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 method 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,

Assignees

• Siluria Technologies Inc

Inventors

• 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

Classifications

• C07C2523/34

  Manganese · CPC title

• C07C2523/10

  of rare earths · CPC title

• C07C2/84 Primary

  catalytic · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• B01J2219/00747

  Catalysts · CPC title