Catalytic upgrading of heavy hydrocarbons

• US 3,923,635 A
• Filed: 06/17/1974
• Issued: 12/02/1975
• Est. Priority Date: 06/17/1974
• Status: Expired due to Term

• Current Assignee: Bernard L. Schulman, Clyde L. Aldridge
• Original Assignee: Bernard L. Schulman, Clyde L. Aldridge
• Inventors: Schulman, Bernard L., Aldridge, Clyde L.
• Primary Examiner(s): Levine, Herbert
• Application Number:
  US05/479,745
• Time in Patent Office: 533 Days
• Field of Search: 208/50,108,127,157,110,112
• US Class Current: 208/50
• CPC Class Codes: C10G 45/16 suspended in the oil, e.g. slurries

Abstract

Heavy mineral oils are upgraded by reaction with hydrogen in the presence of a catalyst comprising a solid carbon-containing material and an alkali metal component. The spent solids are reactivated in a catalytic gasification process.

Claims

1. A PROCESS FOR UPGRADING A HEAVY HYDROCARBON FEED CONTAINING SULFUR CONTAMINANTS, WHICH COMPRISES:

A. CONTACTING SAID HYDROCARBON FEED WITH HYDROGEN AND CATALYST PARTICLES COMPRISING A SOLID CARBON-CONTAINING MATERIAL AND AT LEAST 2 WEIGHT PERCENT OF AN ALKALI METAL COMPONENT (CALCULATED AS THE METAL BASED ON THE CARBONCONTAINING MATERIAL) IN A REACTION ZONE MAINTAINED AT AN AVERAGE TEMPERATURE RANGING FROM ABOUT 700* TO ABOUT 1000*F. AND AT A HYDROGEN PARTIAL PRESSURE OF ABOUT 200 TO 4000 PSIG TO PRODUCE A VAPOROUS PRODUCT COMPRISING NORMALLY LIQUID LIGHT HYDROCARBONS OF REDUCED SULFUR CONTENT, A CARBONACEOUS RESIDUE, AT LEAST A PORTION OF SAID CARBONACEOUS RESIDUE DEPOSITING ON SAID CATALYST PARTICLES, AND HEAVY LIQUID HYDROCARBONS;

B. REMOVING SAID VAPOROUS PRODUCT OVERHEAD FROM SAID REACTIONE ZONE;

C. REMOVING FROM THE BOTTOM OF SAID REACTION ZONE A SLURRY OF A PORTION OF SAID HEAVY LIQUID HYDROCARBONS AND A PORTION OF SAID CATALYST PARTICLES;

D. SEPARATIG THE CATALYST PARTICLES FROM SAID SLURRY;

E. CONTACTING AT LEAST A PORTION OF THE SEPARATED CATALYST PARTICLES WITH STEAM IN A GASIFICATION ZONE OPERATED AT A TEMPERATURES RANGING FROM ABOUT 1000* TO ABOUT 1700*F., WHEREBY AT LEAST A PORTION OF THE CARBONACEOUS DEPOSITION IS CONVERTED TO A GAS COMPRISING HYDROGEN AND CARBON MONOXIDE, AND F. RECYCLING A PORTION OF THE CATALYST PARTICLES FROM THE GASIFICATION ZONE TO SAID REACTION ZONE OF STEP (A).

2. The process of claim 1, wherein said reaction zone of step (a) comprises an ebullient bed.

3. The process of claim 1, wherein the separation of catalyst particles from said slurry comprises passing said catalyst-containing slurry to a separation zone to remove the liquid hydrocarbons, and subsequently passing at least a portion of the separated catalyst particles to said gasification zone of step (d).

4. The process of claim 1, wherein the separation of catalyst particles from said slurry comprises passing the catalyst-containing slurry to a separation zone to remove a substantial portion of the liquid hydrocarbons, and passing the separated catalyst particles to a devolatilization zone containing a fluidized bed of solid particles maintained at a temperature of about 850* to about 1200*F. and at a pressure ranging from about 0 to about 150 psig to dry said separated catalyst particles and, subsequently, passing at least a portion of the dried catalyst particles to the gasification zone of step (d).

5. The process of claim 1, wherein the separation of catalyst particles from said slurry comprises passing sAid catalyst-containing slurry to a fluid coking zone operated at a temperature of about 850* to about 1200*F. and at a pressure ranging from about 0 to 150 psig to volatilize said heavy liquid hydrocarbons and thereby separate said catalyst particles from the slurry, and, subsequently, passing at least a portion of the separated particles to said gasification zone of step (d).

6. The process of claim 1, wherein prior to said steam contacting step (d), said separated catalyst particles are heated in a heating zone.

7. The process of claim 1, wherein said solid carbon-containing material is a solid composition containing less than 1.5 hydrogen atoms per one carbon atom.

8. The process of claim 1, wherein said solid carbon-containing material is selected from the group consisting of coal, coal coke, petroleum coke, activated carbon, lignite, peat, graphite and charcoal.

9. The process of claim 1, wherein said solid carbon-containing material is petroleum coke.

10. The process of claim 1, wherein said catalyst comprises from about 5 to about 20 weight percent of an alkali metal component (calculated as the metal based on said solid carbon-containing material).

11. The process of claim 1, wherein said alkali metal component is a potassium component.

12. The process of claim 1, wherein said alkali metal component is a cesium component.

13. The process of claim 1, wherein said heavy hydrocarbon feed additionally contains metal contaminants.

14. The process of claim 1, wherein said contacting step (a) is conducted in more than one stage.

15. The process of claim 1, wherein said contacting step (a) is conducted at a temperature ranging from about 750* to about 900*F.

16. The process of claim 1, wherein an oxygencontaining gas is introduced into the gasification zone of step (d).

17. The process of claim 1, wherein at least a portion of the hydrogen and carbon monoxide gas formed in the gasification zone is passed to said reaction zone of step (a).

18. The process of claim 1, wherein at least a portion of the hydrogen and carbon monoxide gas formed in the gasification zone is passed to a water gas shift stage to react with steam and form hydrogen and carbon dioxide, separating the hydrogen from the carbon dioxide and passing at least a portion of the separated hydrogen to said reaction zone of step (a).

19. A process for upgrading a heavy hydrocarbon feed containing metal contaminants, which comprises:

a. contacting said hydrocarbon feed with hydrogen and catalyst particles comprising a solid carbon-containing material and at least 2 weight percent of an alkali metal component (calculated as the metal based on the solid carbon-containing material) in an ebullient bed reaction zone maintained at an average temperature ranging from about 750* to about 900*F. and at a hydrogen partial pressure of about 200 to about 4000 psig to produce a vaporous product comprising normally liquid light hydrocarbons of reduced content of metal contaminants, a carbonaceous residue, at least a portion of said carbonaceous residue depositing on said catalyst particles, and heavy liquid hydrocarbons;

b. removing said vaporous product overhead from said ebullient bed reaction zone;

c. removing from the bottom of said ebullient bed reaction zone a slurry of a portion of said heavy liquid hydrocarbons and a portion of said catalyst particles;

d. separating the catalyst particles from said slurry;

e. contacting at least a portion of the separated catalyst particles with steam in a gasification zone operated at a temperature ranging from about 1000* to about 1700*F., whereby at least a portion of the carbonaceous deposition is converted to a gas comprising hydrogen and carbon monoxide, and f. recycling a portion of the catalyst particles from the gasification zone to the ebullient bed reaction zone of step (a).

20. A PROCESS FOR UPGRADING A HEAVY HYDROCARBON FEED CONTAINING SULFUR COMTAMINANTS, WHICH COMPRISES* A. CONTACTING SAID HYDROCARBON FEED WITH HYDROGEN AND CATALYST PARTICLES COMPRISING A SOLID CARBON-CONTAINING MATERIAL AND AT LEAST 2 WEIGHT PERCENT OF AN ALKALI METAL COMPONENT (CALCULATED AS THE METAL BASED ON THE CARBONCONTAINING MATERIAL) IN AN EBULLIENT BED REACTION ZONE MAINTAINED AT AN AVERAGE TEMPERATURE RANGING FROM ABOUT 700* TO ABOUT 1000*F. AND AT A HYDROGEN PARTIAL PRESSURE OF ABOUT 200 TO ABOUT 4000 PSIG, TO PRODUCE A VAPOROUS PRODUCT COMPRISING NORMALLY LIQUID LIGHT HYDROCARBONS OF REDUCED SULFUR CONTENT, A CARBONACEOUS RESIDUE, AT LEAST A PORTION OF SAID CARBONACEOUS RESIDUE DEPOSITING ON SAID CATALYST PARTICLES, AND HEAVY LIQUID HYDROCARBONS;

B. REMOVING SAID VAPOROUS PRODUCT OVERHEAD FROM SAID EBULLIENT BED REACTION ZONE;

C. REMOVING FROM THE BOTTOM OF SAID EBULLIENT BED REACTION ZONE A SLURRY OF A PORTION OF SAID HEAVY LIQUID HYDROCARBONS AND A PORTION OF SAID CATALYST PARTICLES;

D. PASSING SAID CATALYST-CONTAINING SLURRY TO A FLUID COKING ZONE OPERATED AT A TEMPERATURE OF ABOUT 850* TO ABOUT 1200*F. AND AT A PRESSURE RANGING FROM ABOUT 0 TO ABOUT 150 PSIG TO VOLATILIZE SAID HEAVY LIQUID HYDROCARBONS AND THEREBY SEPARATE SAID CATALYST PARTICLES FROM SAID SLURRY;

E. PASSING AT LEAST A PORTION OF THE CATALYST PARTICLES RESULTING FROM STEP (D) TO A GASIFICATION ZONE OPERATED AT A HIGHER TEMPERATURE THAN THE OPERATING TEMPERATURE OF SAID COKING ZONE AND CONTACTING THE SAME WITH STEAM AND AND OXYGEN-CONTAINING GAS, WHEREBY AT LEAST A PORTION OF THE CARBONACEOUS DEPOSITION IS CONVERTED TO A GAS COMPRISING HYDROGEN AND CARBON MONOXIDE;

F. RECYCLING A PORTION OF THE CATALYST PARTICLES FROM THE GASIFICATION ZONE TO THE EBULLIENT BED REACTION ZONE OF STEP (A), AND G. PASSING AN OTHER PORTION OF THE CATALYST PARTICLES FROM THE GASIFICATION ZONE TO THE COKING ZONE.

21. The process of claim 20 wherein said heavy hydrocarbon feed also contains metal contaminants.

22. A process for upgrading a heavy hydrocarbon feed containing sulfur contaminants, which comprises:

a. contacting said hydrcarbon feed with hydrogen and catalyst particles comprising a solid carbon-containing material and at least 2 weight percent of an alkali metal component (calculated as the metal based on the solid carbon-containing material) in an ebullient bed reaction zone maintained at an average temperature ranging from about 700* to about 1000*F. and at a hydrogen partial pressure of about 200 to about 4000 psig, to produce a vaporous product comprising normally liquid light hydrocarbons of reduced sulfur content, a carbonaceous residue, at least a portion of said carbonaceous residue depositing on the catalyst particles, and heavy liquid hydrocarbons;

b. removing said vaporous product overhead from said ebullient bed reaction zone;

c. removing from the bottom of said ebullient bed reacton zone a slurry of a portion of said heavy liquid hydrocarbons and a portion of said catalyst particles;

d. passing said catalyst-containing slurry to a fluid coking zone operated at a temperature ranging from about 850* to about 1200*F. and at a pressure ranging from about 0 to about 150 psig to volatilize said heavy liquid hydrocarbons and thereby separate the catalyst particles from said slurry;

e. passing at least a portion of the catalyst particles from the coking zone to a heating zone operated at a higher temperature than the operating temperature of the coking zone to heat said catalyst particles;

f. passing a portion of the heated catalyst particles to a gasification zone operated at an intermediate temperature between the coking zone temperature and the heating zone temperature and contacting said heated catalyst particles with steam to form a gas comprising hydrogen and carbon monoxide;

g. passing a first portion of catalyst particles from the gasification zone to the heating zone;

h. passing a second portion of catalyst particles from the gasification zone to the coking zone, and i. passing a third portion of catalyst particles from the gasification zone to the ebullient bed reaction zone.

23. The process of claim 22 wherein a substantial portion of the heavy liquid hydrocarbons are removed from the catalyst-containing slurry and the recovered catalyst particles are thereafter passed to said fluid coking zone of step (c).

24. The process of claim 22, wherein at least a portion of the hydrogen and carbon monoxide gas formed in the gasification zone is passed to a water gas shift stage to react with steam and form hydrogen and carbon dioxide, separating the hydrogen from the carbon dioxide and passing at least a portion of the separated hydrogen to said ebullient bed reaction zone.

25. A process for upgrading a heavy hydrocarbon feed containing sulfur contaminants, which comprises:

a. contacting said hydrocarbon feed with hydrogen and catalyst particles consisting essentially of a solid carbon-containing material and at least 2 weight percent of an alkali metal component (calculated as the metal based on the carbon-containing material) in a reaction zone maintained at an average temperature ranging from about 700* to about 1000*F. and at a hydrogen partial pressure of about 200 to 4000 psig to produce a vaporous product comprising normally liquid light hydrocarbons of reduced sulfur content, a carbonaceous residue, at least a portion of said carbonaceous residue depositing on said catalyst particles, and heavy liquid hydrocarbons;

b. removing said vaporous product overhead from said reaction zone;

c. removing from the bottom of said reaction zone a slurry of a portion of said heavy liquid hydrocarbons and a portion of said catalyst particles;

d. separating the catalyst particles from said slurry;

e. contacting at least a portion of the separated catalyst particles with steam in a gasification zone operated at a temperature ranging from about 1000* to about 1700*F., whereby at least a portion of the carbonaceous deposition is converted to a gas comprising hydrogen and carbon monoxide, and f. recycling a portion of the catalyst particles from the gasification zone to said reaction zone of step (a).