Catalytic cracking of undesirable components in a coking process

• US 8,968,553 B2
• Filed: 02/12/2013
• Issued: 03/03/2015
• Est. Priority Date: 11/17/2006
• Status: Active Grant

• Current Assignee: Roger G. Etter
• Original Assignee: Roger G. Etter
• Inventors: Etter, Roger G.
• Primary Examiner(s): MCCAIG, BRIAN A
• Application Number:
  US13/765,449
• Publication Number:
  US 20130213858A1
• Time in Patent Office: 749 Days
• Field of Search: 208/50, 208 52- 53, 208131-132, 423/450, 423453-454, 423/458
• US Class Current: 208/53
• CPC Class Codes: C10B 55/00 Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material cracking oils C10G
• CPC Class Codes: C10B 57/12 Applying additives during coking
• CPC Class Codes: C10G 11/00 Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils cracking in direct contact with molten metals or salts C10G9/34
• CPC Class Codes: C10G 11/14 with preheated moving solid catalysts
• CPC Class Codes: C10G 2300/1059 Gasoil having a boiling range of about 330 - 427 °C
• CPC Class Codes: C10G 2300/1096 Aromatics or polyaromatics
• CPC Class Codes: C10G 2300/701 Use of spent catalysts
• CPC Class Codes: C10G 2300/708 Coking aspect, coke content and composition of deposits
• CPC Class Codes: C10G 2300/80 Additives
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 2300/807 Steam
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/06 Gasoil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 9/005 Coking (in order to produce liquid products mainly)
• CPC Class Codes: F17D 3/00 Arrangements for supervising or controlling working operations
• CPC Class Codes: Y10T 137/0318 Processes

Abstract

Undesirable components of traditional coking processes are selectively cracked or coked in the coking vessel by injecting an additive into the vapors in the coking vessel. The additive contains catalyst(s), seeding agent(s), excess reactant(s), quenching agent(s), carrier(s), or any combination thereof to modify reaction kinetics to preferentially crack (or coke) these undesirable components that typically have a high propensity to coke, and are often precursors to coke in the coking process. These undesirable components can also be very problematic in downstream catalytic cracking processes, significantly contributing to coke on catalyst and catalyst deactivation. Exemplary embodiments of the present invention also provide methods to (1) decrease coke production, (2) increase liquid transportation fuels, (3) control the coke crystalline structure, and (4) control the quantity and quality of volatile combustible materials (VCMs) in the resulting coke. Pet coke from this process may have unique characteristics with substantial utility.

Claims

1. A process comprising introducing an additive comprising catalyst(s) and quenching agent(s) into a coking vessel above a vapor/liquid-solid interface during a coking cycle of a delayed coking process.

2. The process of claim 1 wherein said additive further comprises at least one of seeding agent(s), excess reactant(s), and carrier fluid(s).

3. The process of claim 2 wherein said seeding agent(s) comprises chemical element(s) or chemical compound(s) that is adapted to promote formation of coke by providing a surface for coking reactions and the development of coke crystalline structure, and has physical properties including a liquid droplet, a semi-solid, solid particle, or any combination thereof.

4. The process of claim 2 wherein said seeding agent(s) comprises carbon particles, sodium, calcium, iron, or any combination thereof.

5. The process of claim 4 wherein said carbon particles comprise coke, activated carbon, coal, or any combination thereof.

6. The process of claim 2 wherein said excess reactant(s) comprises chemical compound(s) that is adapted to react with heavy aromatics to form petroleum coke, to react with catalyst to catalytically crack, to react with catalyst to catalytically coke, or any combination thereof, and has physical properties of a liquid, a semi-solid, solid particle, or any combination thereof.

7. The process of claim 2 wherein said excess reactant(s) comprises gas oil, FCCU slurry oil, FCCU cycle oil, extract from an aromatic extraction unit, coker feed, bitumen, other aromatic oil, coke, activated carbon, coal, or any combination thereof.

8. The process of claim 2 wherein said carrier fluid(s) comprises liquid, gas, hydrocarbon vapor, or any combination thereof that is adapted to make the additive easier to introduce into the coking vessel.

9. The process of claim 2 wherein said carrier fluid(s) comprises gas oil, FCCU slurry oil, FCCU cycle oil, other hydrocarbon(s), other oil(s), inorganic liquid(s), water, steam, nitrogen, or combinations thereof.

10. The process of claim 1 wherein said catalyst(s) is an acid-based catalyst that is adapted to provide propagation of carbon-based free radicals that are adapted to initiate cracking reactions.

11. The process of claim 10 wherein said free radicals are comprised of carbonium ions, carbenium ions, or any combination thereof.

12. The process of claim 1 wherein said catalyst(s) comprises alumina, silica, zeolite, calcium, activated carbon, crushed pet coke, or any combination thereof.

13. The process of claim 1 wherein said catalyst(s) is selected from the group consisting of Fluid Catalytic Cracking (FCC) catalysts, zeolite catalysts, FCC equilibrium catalysts, hydrocracking catalysts, new catalysts, spent catalysts, regenerated catalysts, multifunctional catalysts, pulverized catalysts, classified catalysts, impregnated catalysts, or any combination thereof.

14. The process of claim 1 wherein said catalyst(s) has particle size characteristics to prevent entrainment in vapors leaving said coking vessel.

15. The process of claim 1 wherein said catalyst(s) has particle size characteristics to achieve fluidization in the coking vessel and increase residence time.

16. The process of claim 1 wherein said catalyst(s) has particle size characteristics to assure settling to the vapor/liquid interface.

17. The process of claim 1 wherein said catalyst(s) settles to the vapor/liquid interface and continues to promote catalytic cracking and/or coking reactions to produce desired cracked liquids and coke.

18. The process of claim 1 wherein said catalyst(s) is adapted to promote cracking of high boiling point materials below a vapor/liquid interface in a delayed coking process.

19. The process of claim 18 wherein said high boiling point materials are derived from thermal cracking of the coker feed.

20. The process of claim 19 wherein said cracking of hydrocarbons below a vapor/liquid interface in a delayed coking process reduces shot coke production.

21. The process of claim 1 wherein said catalyst(s) has high porosity characteristics to allow larger hydrocarbon molecules easy access to the acid sites.

22. The process of claim 1 wherein said catalyst(s) is adapted to lower an activation energy required for cracking reactions, lower an activation energy required for coking reactions, or any combination thereof.

23. The process of claim 1 wherein said quenching agent(s) is adapted to terminate cracking reactions in a product vapor, thereby reducing excessive cracking of middle distillates to low value gases.

24. The process of claim 1 wherein said additive is adapted to quench cracking reactions of vaporous hydrocarbon compounds with molecular weights less than 300.

25. The process of claim 1 wherein said additive is adapted to quench cracking reactions of vaporous hydrocarbon compounds with molecular weights less than 100.

26. The process of claim 1 wherein said quenching agent(s) comprises liquid, gas, hydrocarbon vapor, or any combination thereof that is adapted to have a net effect of reducing temperature(s) of vapors in the coking vessel.

27. The process of claim 1 wherein said quenching agent(s) comprises gas oils, FCCU slurry oil, FCCU cycle oil, other hydrocarbon(s), other oil(s), inorganic liquid(s), water, steam, nitrogen, or combinations thereof.

28. The process of claim 1 wherein said introduction of said additive promotes conversion of high boiling point compounds.

29. The process of claim 28 wherein said conversion comprises catalytic cracking, catalytic coking, thermal cracking, thermal coking, or any combination thereof.

30. The process of claim 28 wherein said conversion of high boiling point compounds is used to reduce recycle in a coking process, reduce heavy components in coker gas oils, or any combination thereof.

31. The process of claim 28 wherein:

said conversion includes cracking high boiling point compounds to lighter hydrocarbons that leave the coking vessel as vapors and enter a downstream fractionators; and

said lighter hydrocarbons are separated into process streams that are useful in oil refinery product blending.

32. The process of claim 31 wherein said lighter hydrocarbons comprise naphtha, gas oil, gasoline, kerosene, jet fuel, diesel fuel, heating oil, or any combination thereof.

33. The process of claim 28 wherein said conversion includes coking high boiling point compounds to coke in the coking vessel.

34. The process of claim 33 wherein said coke is comprised of Volatile Combustible Materials with theoretical boiling points exceeding 950°

F.

35. The process of claim 34 wherein said coke is comprised of Volatile Combustible Materials with theoretical boiling points exceeding 1250°

F.

36. The process of claim 35 wherein said coke is acceptable quality for calcining.

37. The process of claim 35 wherein said Volatile Combustible Materials are devolatilized from the coke in a calcining zone of a calciner.

38. The process of claim 37 wherein said Volatile Combustible Materials are recoked in a porous structure of the coke to increase coke density.

39. The process of claim 38 wherein said higher density coke is adapted to require less binder in a production of anodes for an aluminum industry.

40. The process of claim 33 wherein said coke comprises minimal Volatile Combustible Materials with theoretical boiling points less than 1780°

F.

41. The process of claim 33 wherein said coke has sponge coke morphology.

42. The process of claim 33 wherein said coke has a Hardgrove Grindability Index of greater than 50.

43. The process of claim 33 wherein said coke has needle coke morphology.

44. The process of claim 43 wherein said coke is acceptable quality for electrodes.