Combination hydroconversion, coking and gasification

• US 4,204,943 A
• Filed: 09/15/1978
• Issued: 05/27/1980
• Est. Priority Date: 03/24/1978
• Status: Expired due to Term

• Current Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Original Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Inventors: Bearden, Roby Jr., Aldridge, Clyde L., Metrailer, William J.
• Primary Examiner(s): Levine, Herbert
• Application Number:
  US05/942,689
• Time in Patent Office: 620 Days
• Field of Search: 208/50, 208/127, 208/8 LE, 208/157
• US Class Current: 208/50
• CPC Class Codes: C10B 55/10 according to the "fluidised bed" technique
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 1/08 with moving catalysts
• CPC Class Codes: C10G 1/083 in the presence of a solvent
• CPC Class Codes: C10G 1/086 Characterised by the catalyst used
• CPC Class Codes: C10G 47/26 suspended in the oil, e.g. slurries
• CPC Class Codes: C10G 69/06 including at least one step of thermal cracking in the absence of hydrogen
• CPC Class Codes: C10J 2300/0906 Physical processes, e.g. shredding, comminuting, chopping, sorting
• CPC Class Codes: C10J 2300/093 Coal
• CPC Class Codes: C10J 2300/0943 Coke
• CPC Class Codes: C10J 2300/0956 Air or oxygen enriched air
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0976 as steam
• CPC Class Codes: C10J 2300/0986 Catalysts
• CPC Class Codes: C10J 2300/1807 Recycle loops, e.g. gas, solids, heating medium, water
• CPC Class Codes: C10J 2300/1884 with one stream being synthesis gas
• CPC Class Codes: C10J 2300/1892 with one stream being water/steam
• CPC Class Codes: C10J 3/482 Gasifiers with stationary fluidised bed
• CPC Class Codes: C10J 3/54 Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
• CPC Class Codes: C10J 3/721 Multistage gasification, e.g. plural parallel or serial gasification stages
• CPC Class Codes: C10J 3/78 : High-pressure apparatus
• CPC Class Codes: C10J 3/84 : with means for removing dust or tar from the gas

Abstract

A combination slurry hydroconversion, coking and coke gasification process is provided wherein carbonaceous solids having an average particle size of less than 10 microns in diameter or the ashes thereof are used as a catalyst in the hydroconversion stage.

Claims

1. A process for upgrading a liquid-containing carbonaceous chargestock which comprises:

(a) adding to said chargestock hydroconversion catalytic solids having an average particle size of less than about 10 microns in diameter to form a mixture, said solids being selected from the group consisting of fluid coke, delayed coke, coal coke, carbonaceous residue derived from the gasification of coke, an ash of said coke, an ash of said carbonaceous residue and mixtures thereof;

(b) reacting the chargestock containing said catalytic solids as a slurry with a molecular hydrogen-containing gas under hydroconversion conditions in a hydroconversion zone to produce an upgraded hydrocarbonaceous oil product;

(c) separating a heavy oil fraction from said hydrocarbonaceous oil product;

(d) subjecting at least a portion of said separated oil fraction to coking conditions in a coking zone to produce coke, and

(e) reacting at least a portion of said coke with steam and a molecular oxygen-containing gas to produce a hot gaseous stream containing hydrogen and a solid carbonaceous residue.

2. The process of claim 1 wherein said coking zone is a delayed coking zone operated at delayed coking conditions.

3. The process of claim 1 wherein said coking zone is a fluid coking zone operated at fluid coking conditions.

4. The process of claim 1 or 2 wherein said carbonaceous residue of step (a) is derived from gasification of delayed coke.

5. The process of claim 1 or 2 wherein said carbonaceous residue is derived from gasification of fluid coke.

21. The process of claim 1 or claim 6 wherein said chargestock comprises a hydrocarbonaceous oil.

22. The process of claim 1 or claim 6 wherein said chargestock comprises coal.

6. A process for upgrading a liquid-containing carbonaceous chargestock which comprises:

(a) adding to said chargestock hydroconversion catalytic solids having an average particle size of less than about 10 microns in diameter to form a mixture, said solids being selected from the group consisting of fluid coke, delayed coke, coal coke, a carbonaceous residue derived from gasification of coke, an ash of said coke, an ash of said carbonaceous residue and mixtures thereof;

(b) reacting the chargestock containing said catalytic solids as a slurry with a molecular hydrogen-containing gas under hydroconversion conditions in a hydroconversion zone to produce an upgraded hydrocarbonaceous oil product;

(c) separating a heavy oil fraction from said hydrocarbonaceous oil product;

(d) contacting at least a portion of said separated heavy oil fraction with a bed of fluidized solids maintained in a fluid coking zone under fluid coking conditions to form coke, said coke depositing on said fluidized solids;

(e) introducing a portion of said solids with a coke deposition thereon into a heating zone operated at a temperature greater than said coking zone temperature to heat said portion of solids;

(f) recycling a first portion of heated solids from said heating zone to said coking zone;

(g) introducing a second portion of said heated solids to a fluid bed gasification zone maintained at a temperature greater than the temperature of said heating zone;

(h) reacting said second portion of heated solids in said gasification zone with steam and a molecular oxygen-containing gas to produce a hot gaseous stream containing hydrogen and a solid carbonaceous residue;

(i) introducing said hot gaseous stream containing hydrogen and entrained solids into said heating zone;

(j) recovering from said heating zone the resulting cooled gaseous stream containing hydrogen and entrained solid carbonaceous fines, and

(k) separating at least a portion of said solid carbonaceous fines from said cooled gaseous stream.

7. The process of claim 6 wherein said carbonaceous residue of step (a) is derived from gasification of delayed coke.

8. The process of claim 6 wherein said carbonaceous residue of step (a) is derived from gasification of fluid coke.

9. The process of claim 6 wherein said solid carbonaceous residue of step (h) is subjected to a particle reduction step to produce particles having an average diameter of less than about 10 microns and wherein at least a portion of the resulting small particles is recycled to said chargestock of step (a).

10. The process of claim 6 wherein said carbonaceous residue of step (h) is burned to produce ash particles having an average particle size of less than about 10 microns in diameter, and wherein at least a portion of the resulting ash particles are recycled to said chargestock of step (a).

11. The process of claim 6 wherein at least a portion of said solid carbonaceous fines of step (k) is recycled to said chargestock of step (a).

12. The process of claim 6 wherein prior to step (b), said mixture of chargestock and carbonaceous solids is treated with a gas comprising hydrogen and from about 1 to about 90 mole percent hydrogen sulfide.

13. The process of claim 12 wherein said treatment is conducted at a temperature ranging from about 615°

to about 980°

F. and at a pressure ranging from about 500 to about 5000 psig.

14. The process of claim 6 wherein said catalytic solids are added to said chargestock in an amount sufficient to provide from about 0.1 to 20 weight percent solids, based on said chargestock.

15. The process of claim 6 wherein said catalytic solids are added to said chargestock in an amount sufficient to provide from about 0.5 to about 10 weight percent solids, based on said chargestock.

16. The process of claim 6 wherein said catalytic solids are added to said chargestock in an amount sufficient to provide from about 1 to about 5 weight percent solids, based on said chargestock.

17. The process of claim 6 wherein said hydroconversion conditions include a temperature ranging from about 650°

F. to about 1000°

F. and a hydrogen partial pressure ranging from about 500 psig to about 5000 psig.

18. The process of claim 6 wherein said hydroconversion conditions include a temperature ranging from about 790°

to about 900°

F. and a hydrogen partial pressure ranging from about 1000 to about 3000 psig.

19. The process of claim 6 wherein said fluid coking conditions include a temperature ranging from about 850°

to about 1400°

F. and a pressure ranging from about 5 to about 150 psig.

20. The process of claim 6 wherein said gasification conditions include a temperature ranging from about 1200°

to about 2000°

F. and a pressure ranging from about 5 to about 150 psig.