Process and catalyst for methane conversion to aromatics

Patent metadata

Field	Value
Publication number	US-9950971-B2
Application number	US-201514738211-A
Country	US
Kind code	B2
Filing date	Jun 12, 2015
Priority date	Jul 23, 2014
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

A process and catalyst for use therein for the production of aromatics via the oxidative coupling of methane and methane co-aromatization with higher hydrocarbons in a single reaction stage. First, methane is partially converted to ethane and ethylene on an OCM catalyst component, and the OCM intermediate mixture containing methane, ethane and ethylene is subsequently converted into aromatics on an aromatization catalyst component. The reaction may be conducted at 550-850° C. and at about 50 psig. The claimed process and catalyst used therein achieves high methane conversion at lower temperatures (less than 800° C.), higher methane conversion into the aromatic products and significant reductions in production cost when compared to the traditional two (or more) step processes.

First claim

What is claimed is:

1. A process for producing aromatics, the process comprising:
a. providing a feed comprising methane and an oxidant, wherein the feed has a mole ratio of methane to oxidant that is about 2:1 to about 20:1;
b. contacting the feed with a catalyst comprising an oxidative coupling of methane (“OCM”) component and an aromatization component under conditions, including a temperature of about 600-800° C., effective to convert at least part of the methane in the feed to a product comprising at least 7 wt. % of aromatics, based on the weight of the product, wherein the OCM catalyst component and aromatization catalyst component are physically mixed within a single reactor or the OCM catalyst component is integrated with the aromatization catalyst component to form a hybrid catalyst, wherein the OCM catalyst component comprises at least one alkaline/rare earth metal oxide, wherein the aromatization catalyst component comprises at least one molecular sieve and at least one dehydrogenation component; and
c. separating at least part of the aromatics from the product.

2. The process of claim 1 , wherein the molecular sieve comprises an aluminosilicate or a substituted aluminosilicate.

3. The process of claim 1 , wherein the molecular sieve has a pore size of about 5.3 to about 5.7 Angstroms.

4. The process of claim 1 , wherein the molecular sieve comprises ZSM-5 or ZSM-11.

5. The process of claim 1 , wherein the dehydrogenation component comprises a metal or compound thereof from Groups 3 to 13 of the Periodic Table.

6. The process of claim 5 , wherein the dehydrogenation component comprises a metal or compound selected from Ga, Zn, In, Sn, Cu, Re, Mo, W, La, Fe, Ag, Pt, Pd and mixtures thereof.

7. The process of claim 1 , wherein the alkaline earth/rare earth metal oxide is selected from the group consisting of Li-supported MgO, Bi-supported CaO, Li-supported CaO, Ce supported MgO, Ni/La-supported MgO, Sr-supported La 2 O 3 , Li-supported La 2 O 3 , and mixtures thereof.

8. The process of claim 1 , wherein the molecular sieve has been selectivated for paraxylene.

9. The process of claim 1 , wherein at least a part of the methane is derived from natural gas.

10. The process of claim 1 , wherein the oxidant is selected from the group consisting of O 2 , air, ozone, peroxides, NO 2 , NO, and N 2 O.

11. A process for producing aromatics, the process comprising contacting a feed comprising methane and an oxidant with a catalyst comprising an oxidative coupling of methane (“OCM”) component and an aromatization component under conditions, including a temperature of about 600-800° C., effective to convert at least part of the methane in the feed to a product comprising at least 7 wt. % of aromatics, based on the weight of the product;
wherein the feed has a mole ratio of methane to oxidant that is about 2:1 to about 20:1;
wherein the OCM catalyst component comprises at least one alkaline/rare earth metal oxide;
wherein the aromatization catalyst component comprises at least one molecular sieve having pores and at least one dehydrogenation component; and
wherein the OCM catalyst component is integrated with the aromatization catalyst component to form a hybrid catalyst by dispersing the OCM catalyst within the pores of the molecular sieve of the aromatization component and formulating the catalyst into an extrudate.

12. The process of claim 11 , wherein the hybrid catalyst is selectivated to increase para-xylene selectivity.

13. The process of claim 11 , further comprising recovering aromatics from the product.

14. The process of claim 11 , wherein the molecular sieve comprises an aluminosilicate or a substituted aluminosilicate.

15. The process of claim 11 , wherein the molecular sieve has a pore size of about 5.3 to about 5.7 Angstroms.

16. The process of claim 11 , wherein the molecular sieve comprises ZSM-5 or ZSM-11.

17. The process of claim 11 , wherein the dehydrogenation component comprises a metal or compound thereof from Groups 3 to 13 of the Periodic Table.

18. The process of claim 17 , wherein the dehydrogenation component comprises a metal or compound selected from Ga, Zn, In, Sn, Cu, Re, Mo, W, La, Fe, Ag, Pt, Pd and mixtures thereof.

19. The process of claim 11 , wherein the alkaline earth/rare earth metal oxide is selected from the group consisting of Li-supported MgO, Bi-supported CaO, Li-supported CaO, Ce supported MgO, Ni/La-supported MgO, Sr-supported La 2 O 3 , Li-supported La 2 O 3 , and mixtures thereof.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Henao Juan D
• Keusenkothen Paul F
• Patil Abhimanyu O

Classifications

• C07C2523/42

  Platinum · CPC title

• C07C2523/18

  Arsenic, antimony or bismuth · CPC title

• C07C2523/08

  of gallium, indium or thallium · CPC title

• C07C2523/02

  of the alkali- or alkaline earth metals or beryllium · CPC title

• Y02P20/52

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