Catalysts for natural gas processes
Catalysts, catalytic forms and formulations, and catalytic methods are provided. The catalysts and catalytic forms and formulations are useful in a variety of catalytic reactions, for example, the oxidative coupling of methane. Related methods for use and manufacture of the same are also disclosed.
1. A catalytic material comprising:
(a) an OCM active catalyst; and
(b) a second catalyst comprising the following formula:
Ln1 a Ln2 b O x (OH) y
wherein:
Ln1 and Ln2 are each independently different lanthanide elements;
O is oxygen;
OH is hydroxy;
a is a number greater than 0; and
b, x and y are each independently numbers of 0 or greater, provided that at least one of x or y is greater than 0, and
wherein the catalytic material comprises a methane conversion of greater than 10% and a C2+selectivity of greater than 50% when the catalytic material is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature ranging from about 550° C. to about 850° C.
2. The catalytic material of claim 1 , wherein b and x are each independently numbers greater than 0, and y is 0.
3. The catalytic material of claim 1 , wherein the OCM active catalyst is a bulk catalyst and the second catalyst is a nanostructured catalyst.
4. The catalytic material of claim 1 , wherein the OCM active catalyst is a nanostructured catalyst.
5. The catalytic material of claim 4 , wherein the OCM active catalyst is a nanowire catalyst.
6. The catalytic material of claim 1 , wherein the second catalyst comprises a nanostructured catalyst comprising a lanthanum/neodymium oxide, a lanthanum/cerium oxide, a neodymium/cerium oxide, a lanthanum/samarium oxide, a neodymium/samarium oxide, a europium/neodymium oxide, a lanthanum/erbium oxide, a neodymium/erbium oxide, or a europium/lanthanum oxide.
7. The catalytic material of claim 1 , wherein the second catalyst comprises a nanostructured catalyst, and Ln1 and Ln2 are each independently lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
8. The catalytic material of claim 1 , wherein the OCM active catalyst comprises titanium, zirconium, hafnium or combinations thereof.
9. The catalytic material of claim 1 , wherein the catalytic material further comprises an alkaline earth metal and one or more lanthanide elements.
10. The catalytic material of claim 9 , wherein the lanthanide elements are selected from Gd and Nd.
11. The catalytic material of claim 9 , wherein the alkaline earth metal is magnesium, calcium, strontium or barium.
12. The catalytic material of claim 1 , wherein the weight ratio of the OCM active catalyst to the second catalyst ranges from about 80% to about 60%.
13. The catalytic material of claim 1 , wherein the crush strength of the catalytic material is greater than about 5 N/mm.
14. The catalytic material of claim 1 , wherein the catalytic material has a volume loss of less than 5% when heated to 900° C. in air for 100 hours.
15. The catalytic material of claim 1 , wherein the OCM activity of the catalytic material is greater than the OCM activity of either (a) or (b) alone.
16. The catalytic material of claim 1 , wherein the OCM active catalyst comprises MgO, La 2 O 3 , Na 2 WO 4 , Mn 2 O 3 , Mn 3 O 4 , Mg 6 MnO 8 , Zr 2 Mo 2 O 8 , NaMnO 4 , Mn 2 O 3 /Na 2 WO 4 , Mn 3 O 4 /Na 2 WO 4 or Na/MnO 4 /MgO, Mn/WO 4 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 or combinations thereof.
17. The catalytic material of claim 1 , wherein the OCM active catalyst further comprises a dopant combination comprising sodium and at least one element from each of groups 2, 16, or combinations thereof.
18. The catalytic material of claim 1 , wherein the catalytic material further comprises a methane conversion of greater than 20% and a C2+selectivity of greater than 50% when the catalytic material is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature ranging from about 550° C. to about 850° C.
19. The catalytic material of claim 1 , wherein the catalytic material further comprises a methane conversion of greater than 10% and a C2+selectivity of greater than 50% when the catalytic material is employed as a heterogeneous catalyst in the oxidative coupling of methane at a feedstock inlet temperature of less than 750° C. measured at an inlet of a reactor comprising the catalytic material.
20. The catalytic material of claim 19 , wherein the C2+selectivity of the catalytic material in the OCM reaction is greater than about 65% when the OCM reaction is conducted at a feedstock inlet temperature of about 600° C. or lower measured at an inlet of a reactor comprising the catalytic material.
21. The catalytic material of claim 1 , wherein the catalytic material further comprises a methane conversion of greater than 20% and a C2+selectivity of greater than 50% when the catalytic material is employed as a heterogeneous catalyst in the oxidative coupling of methane at a feedstock inlet temperature of less than 750° C. measured at an inlet of a reactor comprising the catalytic material.
22. The catalytic material of claim 21 , wherein the C2+selectivity of the catalytic material in the OCM reaction is greater than about 65% when the OCM reaction is conducted at a feedstock inlet temperature of about 600° C. or lower measured at an inlet of a reactor comprising the catalytic material.
23. A formed catalytic material for performing oxidative coupling of methane at linear velocities ranging from about 0.1 m/s to about 10 m/s, the catalytic material comprising:
a) a catalyst;
b) a non-tessellating shape having a plurality of penetrating holes therethrough, the non-tessellating shape selected from the group consisting of an ellipse, a pentagon, and a ring shape;
c) a binder or diluent;
d) a crush strength of greater than about 2 N/mm after exposure to air comprising water at temperatures between about 20° C. and 30° C. for greater than 50 hours; and
d) a bed void fraction of greater than 0.3.
24. A formed catalytic material for performing oxidative coupling of methane at linear velocities ranging from about 0.1 m/s to about 10 m/s, the formed catalytic material comprising (a) a catalyst and a binder or diluent; (b) a non-tessellating shape having a plurality of penetrating holes therethrough, the non-tessellating shape selected from the group consisting of an ellipse, a pentagon, and a ring shape; and (c) at least one rounded or chamfered edge, at least one convex surface or combinations thereof, wherein the catalytic material comprises a methane conversion of greater than 20% and a C2+selectivity of greater than 50% when the catalytic material is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature ranging from about 550° C. to about 850° C.
25. A formed catalytic material for performing oxidative coupling of methane at linear velocities ranging from about 0.1 m/s to about 10 m/s, the formed catalytic material comprising (a) a catalyst and a least one binder or diluent; (b) a non-tessellating shape having a plurality of penetrating holes therethrough, the non-tessellating shape selected from the group consisting of an ellipse, a pentagon, and a ring shape; and (c) at least one rounded or chamfered edge, at least one convex surface or combinations thereof, wherein the catalytic material comprises a methane conversion of greater than 10% and a C2+selectivity of greater than 50% when the catalytic material is employed as a heterogeneous catalyst in the oxidative coupling of methane at a temperature ranging from about 550° C. to about 850° C.