Mixed oxides catalysts for oxidative coupling of methane

Patent metadata

Field	Value
Publication number	US-11458458-B2
Application number	US-201816495554-A
Country	US
Kind code	B2
Filing date	Mar 21, 2018
Priority date	Mar 22, 2017
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

An OCM catalyst composition characterized by general formula AaLabEcDdOx; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and second rare earth element are different; wherein a is 1.0; wherein b is 0.01-10.0; wherein c is 0-10.0; wherein d is 0-10.0; and wherein x balances the oxidation states. The alkaline earth metal is selected from the group consisting of Mg, Ca, Sr, Ba, and combinations thereof. The first rare earth element and the second rare earth element can each independently be selected from the group consisting of Sc, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Y, Tb, Dy, Ho, Er, Tm, Yb, Lu, and combinations thereof. The redox agent is selected from the group consisting of Mn, W, Bi, Sb, Sn, Ce, Pr, and combinations thereof.

First claim

What is claimed is:

1. An oxidative coupling of methane (OCM) catalyst composition characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.

2. The OCM catalyst composition of claim 1 , wherein the alkaline earth metal is selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof.

3. The OCM catalyst composition of claim 1 , wherein the first rare earth element and the second rare earth element can each independently be selected from the group consisting of scandium (Sc), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), yttrium (Y), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and combinations thereof.

4. The OCM catalyst composition of claim 1 , wherein the redox agent is selected from the group consisting of manganese (Mn), tungsten (W), bismuth (Bi), antimony (Sb), tin (Sn), cerium (Ce), praseodymium (Pr), and combinations thereof.

5. The OCM catalyst composition of claim 1 comprising one or more oxides of A; one or more oxides of La; one or more oxides of E; one or more oxides of D; or combinations thereof.

6. The OCM catalyst composition of claim 1 having the general formula Sr a La b Yb c Ce d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

7. The OCM catalyst composition of claim 1 having the general formula Sr a La b Yb c Tm d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

8. The OCM catalyst composition of claim 1 having the general formula A a La b O x ; wherein A is an alkaline earth metal; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

9. The OCM catalyst composition of claim 8 having the general formula Sr a La b O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

10. The OCM catalyst composition of claim 1 having the general formula A a La b E c O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

11. The OCM catalyst composition of claim 10 having the general formula Sr a La b Yb c O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

12. The OCM catalyst composition of claim 1 having the general formula A a La b D d O x ; wherein A is an alkaline earth metal; wherein D is a redox agent; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.

13. The OCM catalyst composition of claim 1 , wherein (1) the OCM catalyst composition is characterized by a C 2+ selectivity that is increased by equal to or greater than about 2%, when compared to a C 2+ selectivity of an otherwise identical OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01:1 to about 10.0:1; and wherein (2) the OCM catalyst composition is characterized by a CH 4 conversion that is increased by equal to or greater than about 1%, when compared to a CH 4 conversion of an otherwise identical OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01:1 to about 10.0:1.

14. The OCM catalyst composition of claim 1 , wherein the OCM catalyst composition is characterized by a reactor temperature effective for achieving an O 2 conversion of equal to or greater than about 90% that is decreased by equal to or greater than about 25° C., when compared to a reactor temperature effective for achieving an O 2 conversion of equal to or greater than about 90% of an otherwise identical OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01:1 to about 10.0:1.

15. A method of making an oxidative coupling of methane (OCM) catalyst composition comprising:
(a) forming an OCM catalyst precursor mixture; wherein the OCM catalyst precursor mixture comprises one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of La to alkaline earth metal of b: 1 , wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: 1 , wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor mixture is characterized by a molar ratio of redox agent or second rare earth element to alkaline earth metal of d: 1 , wherein d is from about 0 to about 10.0; and
(b) calcining at least a portion of the OCM catalyst precursor mixture to form the OCM catalyst composition, wherein the OCM catalyst composition is characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.

16. The method of claim 15 , wherein the step (a) of forming an OCM catalyst precursor mixture further comprises (i) solubilizing the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation in an aqueous medium to form an OCM catalyst precursor aqueous solution; and (ii) drying at least a portion of the OCM catalyst precursor aqueous solution at a temperature of equal to or greater than about 75° C. to form the OCM catalyst precursor mixture.

17. The method of claim 15 , wherein the OCM catalyst precursor mixture is calcined at a temperature of equal to or greater than about 750° C.

18. The method of claim 15 , wherein the one or more compounds comprising an alkaline earth metal cation comprises an alkaline earth metal nitrate, an al

Assignees

• Sabic Global Technologies Bv

Inventors

• Liang Wugeng
• West David
• Li Luanyi
• SARSANI Vidya Sagar Reddy
• Perez Hector
• Kauffman James W

Classifications

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C07C2523/10

  of rare earths · CPC title

• C07C2/84 Primary

  catalytic · CPC title