Zinc containing methane aromatization catalyst, method of making a method of using the catalyst
View Patent ↗A catalyst for converting methane to aromatic hydrocarbons is described herein. The catalyst comprises an active metal or a compound thereof, zinc or a compound thereof and an inorganic oxide support wherein the active metal is added to the support as a metal oxalate. A method of making the catalyst and a method of using the catalyst are also described.
1. A methane aromatization catalyst comprising an active metal or a compound thereof, zinc or a compound thereof and an inorganic oxide support wherein the active metal is added to the support as a metal oxalate and the active metal is not zinc and wherein the active metal comprises molybdenum, wherein the molybdenum concentration in the catalyst is in the range of from 6 to 10% wt, and wherein the zinc is present in an amount of from 0.7 to 2.0% wt.
2. A catalyst as claimed in claim 1 wherein an additional promoter compound is added to the support.
3. A catalyst as claimed in claim 1 wherein the inorganic oxide support is a zeolite or zeolite-containing support.
4. A catalyst as claimed in claim 3 wherein the zeolite is a ZSM-5 type zeolite.
5. A catalyst as claimed in claim 1 wherein the zinc is added as a zinc oxalate.
6. A process for preparing a methane aromatization catalyst comprising: contacting an active metal oxalate with an inorganic oxide support to form a mixture, contacting zinc or a compound thereof with the mixture to form a catalyst precursor and calcining the precursor wherein the active metal oxalate does not comprise zinc and wherein the active metal comprises molybdenum, wherein the molybdenum concentration in the catalyst is in the range of from 6 to 10% wt, and wherein the zinc is present in an amount of from 0.7 to 2.0% wt, and wherein the active metal oxalate is in the form of a solution that is used to impregnate the inorganic support.
7. A process as claimed in claim 6 wherein the zinc is in the form of a solution that is used to impregnate the support.
8. A process as claimed in claim 6 wherein the active metal oxalate and zinc are combined and then contacted with the inorganic oxide support to form the catalyst precursor.
9. A process as claimed in claim 6 wherein the zinc or compound thereof is impregnated on the support and then the active metal oxalate is impregnated on the support.
10. A process as claimed in claim 6 wherein the zinc compound comprises zinc oxalate.
11. A process as claimed in claim 6 wherein the inorganic oxide support is a zeolite or zeolite-containing support.
12. A process as claimed in claim 6 wherein the support comprises ZSM-5 type zeolite.
13. A process as claimed in claim 6 wherein the support contains zeolite and a binder.
14. A process as claimed in claim 6 wherein contacting the metal oxalate with the inorganic oxide support is carried out at a temperature in the range of from 0° C. to 100° C.
15. A process as claimed in claim 6 wherein contacting the metal oxalate with the inorganic oxide support is carried out at a temperature in the range of from 15° C. to 40° C.
16. A process as claimed in claim 6 further comprising a drying step before the calcining.
17. A process as claimed in claim 16 wherein the drying and calcining comprises:
a. subjecting the impregnated support to a temperature of from 70° C. to 120° C. for at least 20 minutes;
b. increasing the temperature at a rate of from 1° C. to 10° C. per minute to a temperature of from 275° C. to 325° C.;
c. maintaining the temperature achieved in step (b) for at least 20 min;
d. increasing the temperature at a rate of from 1° C. to 30° C. per minute to a temperature of from 475° C. to 650° C.; and
e. maintaining the temperature achieved in step (d) for at least 20 min.
18. A process as claimed in claim 16 wherein the drying and calcining comprises:
a. subjecting the impregnated support to a temperature of from 70° C. to 120° C. for from 20 minutes to 240 minutes;
b. increasing the temperature at a rate of from 1° C. to 10° C. per minute to a temperature of from 275° C. to 325° C.;
c. maintaining the temperature achieved in step (b) for from 20 minutes to 240 minutes;
d. increasing the temperature at a rate of from 1° C. to 30° C. per minute to a temperature of from 475° C. to 550° C.; and
e. maintaining the temperature achieved in step (d) for from 20 minutes to 240 minutes.
19. A process as claimed in claim 6 further comprising cooling the impregnated support after calcination.
20. A process for producing aromatic hydrocarbons comprising contacting a gas stream comprising methane with a catalyst comprising molybdenum and zinc wherein the catalyst was prepared by contacting a molybdenum oxalate and a zinc compound with a zeolite-containing support.
21. A process as claimed in claim 20 wherein zinc was added to the catalyst as zinc oxalate.
22. A process as claimed in claim 20 wherein the gas stream comprising methane has a methane concentration of from 75 to 100 volume percent.
23. A process as claimed in claim 20 wherein the gas stream comprising methane is derived from biogas.
24. A process as claimed in claim 20 wherein the gas stream containing methane is stranded natural gas.