Selective Cracking and Coking of Undesirable Components in Coker Recycle and Gas Oils

• US 20100170827A1
• Filed: 11/19/2007
• Published: 07/08/2010
• Est. Priority Date: 11/17/2006
• Status: Active Grant

• Current Assignee: Roger G. Etter
• Original Assignee: Roger G. Etter
• Inventors: Etter, Roger G.
• Granted Patent: US 8,372,265 B2
• Time in Patent Office: Days
• US Class Current: 208/40
• 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 gas oil components are selectively cracked or coked in a coking vessel by injecting an additive into the vapors of traditional coking processes in the coking vessel prior to fractionation. 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. Exemplary embodiments of the present invention also provide methods to control the (1) coke crystalline structure and (2) the quantity and quality of volatile combustible materials (VCMs) in the resulting coke. That is, by varying the quantity and quality of the catalyst, seeding agent, and/or excess reactant the process may affect the quality and quantity of the coke produced, particularly with respect to the crystalline structure (or morphology) of the coke and the quantity & quality of the VCMs in the coke.

Claims

1. A coking process wherein additive comprising catalyst(s), seeding agent(s), excess reactant(s), quenching agent(s), carrier fluid(s), or any combination thereof is injected into vapors leaving a coking vessel above a vapor/liquid-solid interface for selective conversion of high boiling point compounds.

2. A process of claim 1 wherein said catalyst lowers an activation energy required for cracking reactions, coking reactions, or any combination thereof.

3. A process of claim 1 wherein said catalyst is an acid based catalyst that provides propagation of carbon based free radicals that initiate cracking and coking reactions.

4. A process of claim 3 wherein said free radicals are comprised of carbonium ions, carbenium ions, or any combination thereof.

5. A process of claim 1 wherein said catalyst comprises alumina, silica, zeolite, calcium, activated carbon, crushed pet coke, or any combination thereof.

6. A process of claim 1 wherein said catalyst comprises new catalyst, FCCU equilibrium catalyst, spent catalyst, regenerated catalyst, pulverized catalyst, classified catalyst, impregnated catalysts, treated catalysts, or any combination thereof.

7. A process of claim 1 wherein said seeding agent comprises any chemical element(s) or chemical compound(s) that enhances a 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.

8. A process of claim 1 wherein said seeding agent comprises said catalyst of claim 6, carbon particles, sodium, calcium, iron, or any combination thereof.

9. A process of claim 8 wherein said carbon particles comprise coke, activated carbon, coal, carbon black, or any combination thereof.

10. A process of claim 1 wherein said excess reactant comprises any chemical compound(s) that reacts with heavy aromatics to form petroleum coke, reacts with catalyst to catalytically crack, reacts 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.

11. A process of claim 1 wherein said excess reactant 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, carbon black, or any combination thereof.

12. A process of claim 1 wherein said carrier fluid comprises any liquid, gas, hydrocarbon vapor, or any combination thereof that makes the additive easier to inject into the coking vessel.

13. A process of claim 1 wherein said carrier fluid comprises gas oil, FCCU slurry oil, FCCU cycle oil, other hydrocarbon(s), other oil(s), inorganic liquid(s), water, steam, nitrogen, or combinations thereof.

14. A process of claim 1 wherein said additive quenches cracking reactions of vaporous hydrocarbon compounds with molecular weights less than 300.

15. A process of claim 14 wherein said additive quenches cracking reactions of vaporous hydrocarbon compounds with molecular weights less than 100.

16. A process of claim 1 wherein said quenching agent comprises any liquid, gas, hydrocarbon vapor, or any combination thereof that has a net effect of further reducing temperature(s) of vapors exiting the coking vessel.

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

18. A process of claim 1 wherein said selective conversion comprises catalytic cracking, catalytic coking, thermal cracking, thermal coking, or any combination thereof.

19. A process of claim 1 wherein said selective 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.

20. A process of claim 1 wherein said selective conversion includes cracking high boiling point compounds to lighter hydrocarbons that leave the coking vessel as vapors and enter a downstream fractionator where said lighter hydrocarbons are separated into process streams that are useful in oil refinery product blending.

21. A process of claim 20 wherein said lighter hydrocarbon streams comprise naphtha, gas oil, gasoline, kerosene, jet fuel, diesel fuel, heating oil, or any combination thereof.

22. A process of claim 1 wherein said selective conversion includes coking high boiling point compounds to coke in the coking vessel.

23. A process of claim 22 wherein said coke is preferentially comprised of Volatile Combustible Materials with theoretical boiling points exceeding 950°

F.

24. A process of claim 22 wherein said coke is preferentially comprised of Volatile Combustible Materials with theoretical boiling points exceeding 1250°

F.

25. A product of claim 24 wherein said coke is acceptable quality for calcining.

26. A product of claim 25 wherein said Volatile Combustible Materials are preferentially devolatilized from the coke in a calcining zone (not an upheat zone) of a calciner.

27. A product of claim 26 wherein said Volatile Combustible Materials are recoked in a porous structure of the coke to increase coke density.

28. A product of claim 27 wherein said higher density coke requires less binder in a production of anodes for an aluminum industry.

29. A process of claim 22 wherein said coke preferentially contains minimal Volatile Combustible Materials with theoretical boiling less than 1780°

F.

30. A process of claim 22 wherein said coke is preferentially coked with sponge coke morphology.

31. A product of claim 22 wherein said coke has a Hardgrove Grindability Index of greater than 50.

32. A process of claim 22 wherein said coke is preferentially coked with needle coke morphology.

33. A product of claim 32 wherein said coke is acceptable quality for electrodes.

34. A process of claim 1, wherein said catalyst has particle size characteristics to prevent entrainment in the vapor product.

35. A process of claim 1, wherein said catalyst has particle size characteristics to achieve fluidization in the coking vessel and increase residence time in said product vapors.

36. A process of claim 1, wherein said coking vessel has cyclones to minimize entrainment of said catalyst in said product vapors.