Catalysts for petrochemical catalysis

Patent metadata

Field	Value
Publication number	US-10654769-B2
Application number	US-201815944665-A
Country	US
Kind code	B2
Filing date	Apr 3, 2018
Priority date	May 24, 2011
Publication date	May 19, 2020
Grant date	May 19, 2020

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 catalyst comprising a mixed oxide of a lanthanide and tungsten, wherein the catalyst further comprises a sodium dopant and at least one doping element from groups 2, 4-15, lanthanides or combinations thereof, wherein the catalyst 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 lanthanide is Ce, Pr, Nd, La, Eu, Sm or Yb.

3. The catalyst of claim 1 , wherein the at least one doping element is Fe, Co, Mn, Cu, Ni, Sr, Ga, Zr, Pb, Zn, Cr, Pt, Al, Nb, La, Ba, Bi, Sn, In, Ru, P or combinations thereof.

4. 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.

5. 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.

6. The catalyst of claim 1 , wherein the C 2 yield is greater than 15% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750° C. or less.

7. The catalyst of claim 1 , wherein the methane conversion is greater than 30% when the catalyst is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750° C. or less.

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

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

10. The catalyst of claim 1 in combination with a support material.

11. The catalyst of claim 10 , 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.

12. A method for preparing a downstream product of ethylene, the method comprising converting ethylene into a downstream product of ethylene, wherein the ethylene has been prepared via a reaction employing a catalyst according to claim 1 .

13. The method of claim 12 , wherein the downstream product of ethylene is low density polyethylene, high density polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinyl acetate.

14. The method of claim 12 , wherein the downstream product of ethylene comprises 1-hexene, 1-octene, hexane, octane, benzene, toluene, xylene or combinations thereof.

15. A method for the preparation of a downstream product of ethane, ethylene or combinations thereof, the method comprising converting methane into ethane, ethylene or combinations thereof in the presence of the catalyst of claim 1 and further oligomerizing the ethylene to prepare a downstream product of ethylene.

16. The method of claim 15 , wherein the downstream product of ethylene is low density polyethylene, high density polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinyl acetate.

17. The method of claim 15 , wherein the downstream product of ethylene comprises 1-hexene, 1-octene, hexane, octane, benzene, toluene, xylene or combinations thereof.

18. A method for the preparation of ethane, ethylene or combinations thereof, the method comprising contacting the catalyst of claim 1 with a gas comprising methane at a temperature of 750° C. or less.

19. A catalyst comprising a rare earth oxide and two or more dopants, wherein the catalyst 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, and wherein the dopant comprises Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, 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, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, 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, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Sr/Hf or combinations thereof.

20. The catalyst of claim 19 , wherein the rare earth oxide is a rare earth mixed oxide comprising two or more rare earth elements.

21. The catalyst of claim 20 , wherein the rare earth elements are selected from the group consisting of La, Nd, Eu, Sm, Yb, Gd and Y.

22. The catalyst of claim 19 , where the rare earth oxide comprises a mixed oxide of Y—La, Zr—La, Pr—La, Ce—La or combinations thereof.

23. The catalyst of claim 19 , wherein the rare earth oxide comprises La 4-x Ln x O 6 , wherein x is a number ranging from greater than 0 and less than 4, and Ln is Nd, Eu, Sm, Yb, Gd or Y.

24. The catalyst of claim 23 , wherein Ln is Nd.

25. The catalyst of claim 23 , wherein Ln is Eu.

26. The catalyst of claim 23 , wherein Ln is Sm.

27. The catalyst of claim 23 , wherein Ln is Yb.

28. The catalyst of claim 23 , wherein Ln is Gd.

29. The catalyst of claim 23 , wherein Ln is Y.

30. The catalyst of claim 19 , wherein the rare earth oxide comprises La 2 O 3 , Nd 2 O 3 , Yb 2 O 3 , Eu 2 O 3 , Sm 2 O 3 , Pr 2 O 3 or combinations thereof.

31. The catalyst of claim 19 , wherein the catalyst comprises a dopant combination selected from the group consisting of Sr/Sm, Sr/W, Sb/W, Eu/Na, Sr/Na, Mg/Na, Ca/Sr/W, Sr/W/Li and Sr/Sn.

32. The catalyst of claim 31 , wherein the dopant is Sr/Sm.

33. The catalyst of claim 31 , wherein the dopant is Sr/W.

34. The catalyst of claim 31 , wherein the dopant is Sb/W.

35. The catalyst of claim 31 , wherein the dopant is Eu/Na.

36. The catalyst of claim 31 , wherein the dopant is Sr/Na.

37. The catalyst of claim 31 , wherein the dopant is Mg/Na.

38. The catalyst of claim 31 , wherein the do

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

• B01J27/16

  containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr} · CPC title

• B01J23/54

  combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 · CPC title

• B01J23/63

  with rare earths or actinides · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• C07C2523/10

  of rare earths · CPC title