Combination hydroconversion, fluid coking and gasification

• US 4,178,227 A
• Filed: 06/07/1978
• Issued: 12/11/1979
• 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:
  US05/913,394
• Time in Patent Office: 552 Days
• Field of Search: 208/50, 208/127
• 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 1/086 Characterised by the catalyst used
• CPC Class Codes: C10G 47/20 the catalyst containing other metals or compounds thereof
• 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 solid fines having an average particle size of less than 10 microns in diameter or the ashes thereof recovered from a gaseous product derived from the coke gasification are used as a catalyst in the hydroconversion stage in combination with a catalyst produced from an oil soluble metal compound in situ in the chargestock of the hydroconversion zone.

Claims

1. A process for upgrading a carbonaceous chargestock, which comprises:

(a) adding to said carbonaceous chargestock an oil soluble metal compound of a metal selected from the group consisting of Groups IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements and mixtures thereof;

(b) converting said oil soluble metal compound to a solid catalyst within said chargestock in the presence of a hydrogen-containing gas by heating said chargestock to an elevated temperature;

(c) reacting the chargestock containing said catalyst with hydrogen under hydroconversion conditions, in a hydroconversion zone to produce an upgraded hydrocarbonaceous oil product;

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

(e) contacting at least a portion of said 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;

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

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

(h) 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;

(i) 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;

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

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

(l) separating at least a portion of said solid carbonaceous fines from said cooled gaseous stream, said separated fines having an average particle size of less than 10 microns in diameter, and

(m) recycling at least a portion of said separated fines to such chargestock of step (a).

2. The process of claim 1 wherein said addition of said oil soluble compound to said chargestock is discontinued after said portion of separated fines is recycled to said chargestock.

3. The process of claim 1 wherein prior to step (c) said chargestock is treated with gas comprising hydrogen and from about 1 to about 90 mole percent hydrogen sulfide.

4. The process of claim 3 wherein said treatment is conducted at a temperature ranging from about 615°

to about 780°

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

5. The process of claim 1 wherein prior to adding said solid carbonaceous fines to said chargestock, the fines are burned to reduce the concentration of carbon of said fines and to produce an ash and, thereafter, adding the resulting ash to said chargestock.

6. The process of claim 1 wherein said solid fines are added to said chargestock in an amount sufficient to provide from about 0.05 to 10 weight percent solid fines based on said chargestock.

7. The process of claim 1 wherein said solid fines are added to said chargestock in an amount sufficient to provide from about 0.10 to about 5 weight percent solid fines based on said chargestock.

8. The process of claim 1 wherein said solid fines are added to said chargestock in an amount sufficient to provide from about 0.20 to about 2 weight percent solid fines based on said chargestock.

9. The process of claim 1 wherein said hydroconversion conditions include a temperature from about 650°

F. to about 1000°

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

10. The process of claim 1 wherein said hydroconversion conditions include a temperature ranging from about 775°

to about 900°

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

11. The process of claim 1 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.

12. The process of claim 1 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.

13. The process of claim 1 wherein said chargestock comprises a hydrocarbonaceous oil.

14. The process of claim 1 wherein said chargestock comprises a coal.

15. The process of claim 1 wherein said chargestock comprises a mixture of hydrocarbonaceous oil and coal.

16. The process of claim 1 wherein said oil soluble metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organometallic compounds and salts of organic amines.

17. The process of claim 1 wherein said oil soluble metal compound is selected from the group consisting of salts of acyclic aliphatic carboxylic acids and salts of alicyclic aliphatic carboxylic acids.

18. The process of claim 1 wherein said oil soluble metal compound is a salt of a naphthenic acid.

19. The process of claim 1 wherein the metal constituent of oil soluble metal compound is selected from the group consisting of molybdenum, chromium and vanadium.

20. The process of claim 1 wherein said oil soluble metal compound is molybdenum naphthenate.

21. The process of claim 1 wherein said oil soluble metal compound is added to said carbonaceous chargestock in an amount ranging from about 10 to about 950 wppm, calculated as the elemental metal, based on said chargestock.