Method for producing olefins using a doped catalyst

• US 7,943,038 B2
• Filed: 01/29/2008
• Issued: 05/17/2011
• Est. Priority Date: 01/29/2008
• Status: Active Grant

• Current Assignee: Kellogg Brown & Root LLC (KBR Incorporated)
• Original Assignee: Kellogg Brown & Root LLC (KBR Incorporated)
• Inventors: Ramamurthy, Pritham
• Primary Examiner(s): Caldarola; Glenn A
• Assistant Examiner(s): Etherton; Bradley
• Application Number:
  US12/021,364
• Publication Number:
  US 20090192343A1
• Time in Patent Office: 1,204 Days
• Field of Search: 585/648, 585/650, 585/651, 585/653, 208/106, 208/113, 208/121, 208/122, 208/118, 208/119, 208/120.01, 208/120.25, 208/120.35
• US Class Current: 208/119
• CPC Class Codes: B01J 29/061 containing metallic elements added to the zeolite
• CPC Class Codes: B01J 29/068 Noble metals
• CPC Class Codes: B01J 29/405 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• CPC Class Codes: B01J 29/90 Regeneration or reactivation
• CPC Class Codes: B01J 38/30 in gaseous suspension, e.g. fluidised bed
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 11/06 Propene
• CPC Class Codes: C07C 2529/08 of the faujasite type, e.g. type X or Y
• CPC Class Codes: C07C 2529/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• CPC Class Codes: C07C 4/06 Catalytic processes C07C4/025 takes precedence
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

Processes for producing one or more olefins are provided. In one or more embodiments, a doped catalyst can be prepared by fluidizing one or more coked-catalyst particles in the presence of one or more oxidants to provide a fluidized mixture. At least a portion of the coke can be removed from the coked-catalyst particles to provide regenerated catalyst particles. One or more doping agents can be distributed throughout the fluidized mixture, depositing on the surface of the regenerated catalyst particles to provide doped catalyst particles. One or more hydrocarbon feeds can be fluidized with the doped catalyst particles to provide a reaction mixture which can be cracked to provide a first product containing propylene, ethylene, and butane.

Claims

1. A process for producing one or more olefins, comprising:

doping a hydrocarbon cracking catalyst, comprising;

fluidizing one or more coked-catalyst particles in the presence of one or more oxidants to provide a fluidized mixture;

removing at least a portion of the coke from the one or more coked-catalyst particles to provide regenerated catalyst particles within the fluidized mixture;

distributing one or more doping agents to the fluidized mixture;

depositing the one or more doping agents onto a surface of the regenerated catalyst particles to provide doped catalyst particles;

forming a reaction mixture comprising one or more hydrocarbon feeds and the doped catalyst particles;

cracking at least a portion of the reaction mixture to provide a first product comprising propylene, ethylene, and butane;

selectively separating at least a portion of the first product to provide a second product comprising propylene and a first recycle comprising butane; and

recycling at least a portion of the first recycle to the one or more hydrocarbon feeds.

2. The process of claim 1, wherein the one or more doping agents comprises magnesium, barium, gallium, ruthenium, rhodium, palladium, or mixtures thereof.

3. The process of claim 1, further comprising increasing a temperature of the fluidized mixture above 480°

C. prior to distributing the one or more doping agents.

4. The process of claim 1, wherein the hydrocarbon cracking catalyst comprises one or more zeolites, faujasite zeolites, modified faujasite zeolites, Y-type zeolites, ultrastable Y-type zeolites (USY), rare earth exchanged Y-type zeolites (REY), rare earth exchanged ultrastable Y-type zeolites (REUSY), rare earth free Z-21, Socony Mobil #5 zeolite (ZSM-5), high activity zeolite catalysts, or any combination thereof.

5. The process of claim 1, wherein the one or more hydrocarbon feeds comprises methane, ethane, propane, butane, and pentane.

6. The process of claim 1, wherein the first product further comprises aromatic hydrocarbons, and wherein the first product comprises at least 10 wt % ethylene and at least 15 wt % aromatic hydrocarbons based on a weight of the one or more hydrocarbon feeds.

7. The process of claim 1, wherein the first product further comprises aromatic hydrocarbons, and wherein the first product comprises at least 10 wt % ethylene, at least 25 wt % propylene, and at least 15 wt % aromatic hydrocarbons based on a weight of the one or more hydrocarbon feeds.

8. The process of claim 1, wherein the doped catalyst particles produce about 10% or more ethylene in the first product relative to the regenerated catalyst particles without the one or more doping agents deposited thereon.

9. The process of claim 1, wherein the one or more doping agents increase an amount of ethylene and an amount of aromatic hydrocarbons and decrease an amount of propylene in the first product relative to the regenerated catalyst particles without the one or more doping agents deposited thereon.

10. The process of claim 1, wherein the doped catalyst particles contain about 0.2 wt % of the one or more doping agents based on a weight of the doped catalyst particles.

11. The process of claim 1, wherein the one or more doping agents is distributed to the fluidized mixture in the form of a mixture comprising the one or more doping agents and a supplemental fuel.

12. A process for producing one or more olefins, comprising:

doping a hydrocarbon cracking catalyst, comprising;

fluidizing one or more coked-catalyst particles in the presence of one or more oxidants to provide a fluidized mixture;

removing at least a portion of the coke from the one or more coked-catalyst particles to provide regenerated catalyst particles within the fluidized mixture;

distributing one or more doping agents to the fluidized mixture;

depositing the one or more doping agents onto a surface of the regenerated catalyst particles to provide doped catalyst particles;

forming a reaction mixture comprising one or more hydrocarbon feeds and the doped catalyst particles;

cracking at least a portion of the reaction mixture in a first reaction zone to provide a first product comprising propylene, ethylene, and butane;

cracking a refinery hydrocarbon comprising gas oil, full range gas oil, resid, or a combination thereof in a second reaction zone to provide a cracked hydrocarbon comprising ethylene, propylene, or a combination thereof;

combining the first product and the cracked hydrocarbon to form a first mixture;

selectively separating at least a portion of the first mixture to provide a second product comprising propylene and a first recycle comprising butane; and

recycling at least a portion of the first recycle to the one or more hydrocarbon feeds.

13. The process of claim 12, wherein the first reaction zone is a first riser operating at a first temperature and a first pressure on a fluidized catalytic cracker;

wherein the second reaction zone is a second riser operating at a second temperature and second pressure on the fluidized catalytic cracker; and

wherein the first product and cracked hydrocarbon are combined within the fluidized catalytic cracker.

14. The process of claim 12, wherein the first reaction zone is a first riser operating at a first temperature and first pressure on a first fluidized catalytic cracker;

wherein the second reaction zone is a first riser operating at a second temperature and second pressure on a second fluidized catalytic cracker; and

wherein the first product and cracked hydrocarbon are combined outside of the first fluidized catalytic cracker and the second fluidized catalytic cracker.

15. The process of claim 12, wherein the one or more doping agents comprises magnesium, barium, gallium, ruthenium, rhodium, palladium, or mixtures thereof.

16. The process of claim 12, further comprising increasing a temperature of the fluidized mixture above 480°

C. prior to distributing the one or more doping agents.

17. The process of claim 12, wherein the hydrocarbon cracking catalyst comprises one or more zeolites, faujasite zeolites, modified faujasite zeolites, Y-type zeolites, ultrastable Y-type zeolites (USY), rare earth exchanged Y-type zeolites (REY), rare earth exchanged ultrastable Y-type zeolites (REUSY), rare earth free Z-21, Socony Mobil #5 zeolite (ZSM-5), high activity zeolite catalysts, or any combination thereof.

18. The process of claim 12, wherein at least one of the one or more hydrocarbon feeds comprises methane, ethane, propane, butane, and pentane.

19. A process for producing one or more olefins, comprising:

doping a hydrocarbon cracking catalyst, comprising;

fluidizing one or more coked-catalyst particles in the presence of one or more oxidants to provide a fluidized mixture;

removing at least a portion of the coke from the one or more coked-catalyst particles to provide regenerated catalyst particles within the fluidized mixture;

distributing one or more doping agents to the fluidized mixture;

depositing the one or more doping agents onto a surface of the regenerated catalyst particles to provide doped catalyst particles;

forming a reaction mixture comprising one or more hydrocarbon feeds and the doped catalyst particles;

cracking at least a portion of the reaction mixture in a first cracker to provide a first product comprising propylene, ethylene, and butane;

cracking a refinery hydrocarbon comprising gas oil, full range gas oil, resid, or a combination thereof in a second cracker to provide a cracked hydrocarbon comprising ethylene, propylene, or a combination thereof;

cracking one or more alkanes in a third cracker to provide an effluent comprising ethylene and propylene;

combining the first product and the cracked hydrocarbon to form a first mixture;

selectively separating at least a portion of the first mixture to provide a second product comprising propylene and a first recycle comprising butane; and

recycling at least a portion of the first recycle to the one or more hydrocarbon feeds.

20. The process of claim 19, further comprising

recycling at least a portion of the first recycle to the first product.

21. The process of claim 19, further comprising combining the effluent with the first mixture prior to selectively separating the first mixture.

22. The process of claim 19, wherein the one or more doping agents comprises magnesium, barium, gallium, ruthenium, rhodium, palladium, or mixtures thereof.

23. The process of claim 19, further comprising increasing a temperature of the fluidized mixture above 480°

C. prior to distributing the one or more doping agents.

24. The process of claim 19, wherein the hydrocarbon cracking catalyst comprises one or more zeolites, faujasite zeolites, modified faujasite zeolites, Y-type zeolites, ultrastable Y-type zeolites (USY), rare earth exchanged Y-type zeolites (REY), rare earth exchanged ultrastable Y-type zeolites (REUSY), rare earth free Z-21, Socony Mobil #5 zeolite (ZSM-5), high activity zeolite catalysts, or any combination thereof.

25. The process of claim 19, wherein at least one of the one or more hydrocarbon feeds comprises methane, ethane, propane, butane, and pentane.

26. The process of claim 19, wherein selectively separating at least a portion of the first mixture further provides a second recycle comprising methane;

and the process further comprises recycling at least a portion of the second recycle to the one or more hydrocarbon feeds.

27. The process of claim 19, wherein selectively separating at least a portion of the first mixture further provides a second recycle comprising about 70 wt % or more methane;

and the process further comprises recycling about 15 vol % to about 35 vol % of the second recycle to the one or more hydrocarbon feeds.

28. The process of claim 19, further comprising recycling about 10 vol % or more of the first product to the one or more hydrocarbon feeds.