Methods and apparatus for separating Fischer-Tropsch catalysts from liquid hydrocarbon product

• US 6,114,399 A
• Filed: 02/06/1997
• Issued: 09/05/2000
• Est. Priority Date: 10/27/1993
• Status: Expired due to Fees

• Current Assignee: North Carolina State University (University of North Carolina System)
• Original Assignee: North Carolina State University (University of North Carolina System)
• Inventors: Roberts, George W., Kilpatrick, Peter K.
• Primary Examiner(s): PADMANABHAN, SREENIVASAN
• Application Number:
  US08/796,375
• Time in Patent Office: 1,307 Days
• Field of Search: 518/700, 518/724, 518/710, 252/373, 502/22, 502/29, 502/326
• US Class Current: 518/710
• CPC Class Codes: B01J 8/228 externally, i.e. the particles leaving the vessel and subsequently re-entering it
• CPC Class Codes: C07C 1/0425 Catalysts; their physical properties
• CPC Class Codes: C07C 1/0485 Set-up of reactors or accessories; Multi-step processes
• CPC Class Codes: C07C 7/10 by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids

Abstract

A method of separating a Fischer-Tropsch catalyst from the output slurry of a Fischer-Tropsch bubble column reactor, where the slurry comprises Fischer-Tropsch catalyst particles and liquid hydrocarbon product is disclosed. The method comprises contacting a compressed hydrocarbon solvent (e.g., a supercritical hydrocarbon solvent, or liquid hydrocarbon solvent which may be at near supercritical conditions) with the output slurry at a temperature and pressure where the liquid hydrocarbon product is soluble in the solvent to form a concentrated slurry phase containing the catalyst particles, and an enriched solvent phase containing liquid hydrocarbon product. This contacting step is then followed by the step of separating the concentrated slurry from the enriched solvent. Apparatus for carrying out the method of the invention is also disclosed.

Claims

1. A method of separating a particle-free hydrocarbon product from the output slurry of a Fischer-Tropsch bubble column reactor, said slurry comprising Fischer-Tropsch catalyst particles and liquid hydrocarbon, said method comprising:

contacting a compressed hydrocarbon solvent with said output slurry at a temperature of from 150 to 400 degrees centigrade and at a pressure of from 10 to 100 atmospheres, said hydrocarbon solvent comprising C4 to C12 hydrocarbon, whereby said liquid hydrocarbon product is soluble in said solvent to form a concentrated slurry phase containing said catalyst particles and an enriched solvent phase containing liquid hydrocarbon product;

separating said concentrated slurry from said enriched solvent;

separating a first fraction of said liquid hydrocarbon product from said enriched solvent to form a first hydrocarbon product fraction and a first depleted solvent;

compressing at least a portion of said first depleted solvent to form a compressed hydrocarbon solvent; and

then

recycling said compressed hydrocarbon solvent to said contacting step; and

recycling said concentrated slurry to said Fischer-Tropsch bubble column reactor;

wherein said first hydrocarbon product fraction contains not more than 100 parts per million of said Fischer-Tropsch catalyst particles.

2. A method according to claim 1, wherein said contacting step is carried out in a mixer and said separating step is carried out in a settler or centrifuge.

3. A method according to claim 1, wherein said contacting step and said separating step are carried out in a continuous countercurrent contactor.

4. A method according to claim 1, wherein said contacting step is carried out with a supercritical hydrocarbon solvent.

5. A method according to claim 1, wherein said contacting step is carried out with a liquid hydrocarbon solvent.

6. A method according to claim 1, wherein said contacting step is carried out with a liquid hydrocarbon solvent, which liquid hydrocarbon solvent is at near-supercritical conditions.

7. A method according to claim 1, wherein said contacting step is carried out at a pressure above the critical pressure of said solvent.

8. A method according to claim 1, wherein said contacting step is carried out at a pressure below the critical pressure of said solvent.

9. A method according to claim 1, wherein said hydrocarbon solvent comprises a fraction of said output slurry.

10. A method according to claim 1, wherein said hydrocarbon solvent consists essentially of a fraction of said output slurry.

11. A method according to claim 1, wherein said hydrocarbon solvent comprises C6 to C8 hydrocarbon.

12. A method according to claim 1, wherein said contacting step is carried out at a temperature of from 200 to 300 degrees centigrade and at a pressure of from 30 to 80 atmospheres.

13. A method according to claim 1, wherein said hydrocarbon solvent and said output slurry are contacted at a ratio, by volume, of from about one to one hundred parts hydrocarbon solvent to one part output slurry.

14. A method according to claim 1, wherein said output slurry has a viscosity of about 1 to 20 centipoise at said contacting step.

15. A method according to claim 1, wherein said output slurry contains from about 10,000 to 400,000 parts per million (ppm) of Fischer-Tropsch catalyst particles.

16. A method according to claim 1, wherein said Fischer-Tropsch catalyst particles are from about 0.1 to 20 microns in diameter.

17. A method according to claim 1, wherein said step of separating a first fraction of liquid hydrocarbon is carried out by (i) reducing the pressure of said enriched solvent at constant temperature, (ii) raising the temperature of said enriched solvent at constant pressure, or (iii) reducing the pressure and raising the temperature of said enriched solvent.

18. A method according to claim 1, further comprising the step of:

separating a second fraction of said liquid hydrocarbon product from said depleted solvent to form a second hydrocarbon product fraction and a second depleted solvent.

19. A method according to claim 18, further comprising the steps of:

compressing at least a portion of said second depleted solvent to form a compressed hydrocarbon solvent; and

then

recycling said compressed hydrocarbon solvent to said contacting step.

20. A method according to claim 18, further comprising the step of:

recycling a portion of said second hydrocarbon product fraction to said bubble column reactor so that the viscosity of the slurry in said bubble column reactor is maintained.

21. A method of making a hydrocarbon product by a Fisher-Tropsch reaction, comprising:

reacting a synthesis gas in the presence of Fisher-Tropsch catalyst particles in a Fischer-Tropsch slurry bubble column reactor to produce a liquid hydrocarbon product in said reactor and an output slurry comprising Fischer-Tropsch catalyst particles and said liquid hydrocarbon product;

contacting a compressed hydrocarbon solvent with said output slurry at a temperature of from 150 to 400 degrees centigrade and at a pressure of from 10 to 100 atmospheres, said hydrocarbon solvent comprising C4 to C12 hydrocarbon, wherein said liquid hydrocarbon product is soluble in said solvent to form a concentrated slurry phase containing said catalyst particles and an enriched solvent phase containing liquid hydrocarbon product;

separating said concentrated slurry from said enriched solvent;

recycling said concentrated slurry to said Fischer-Tropsch bubble column reactor;

separating a first fraction of said liquid hydrocarbon product from said enriched solvent to form a first hydrocarbon product fraction and a first depleted solvent;

compressing at least a portion of said first depleted solvent to form a compressed hydrocarbon solvent; and

recycling said compressed hydrocarbon solvent to said contacting step.

22. A method according to claim 21, further comprising the step of:

separating a second fraction of said liquid hydrocarbon product from said depleted solvent stream to form a second hydrocarbon product fraction and a second depleted solvent.

23. A method according to claim 22, further comprising the steps of:

compressing at least a portion of said second depleted solvent to form a compressed hydrocarbon solvent; and

then

recycling said compressed hydrocarbon solvent to said contacting step.

24. A method according to claim 22, further comprising the step of:

recycling a portion of said second hydrocarbon product fraction to said bubble column reactor, wherein the viscosity of the slurry in said bubble column reactor is maintained.

25. A method according to claim 21, wherein said step of separating a first fraction of liquid hydrocarbon is carried out by (i) reducing the pressure of said enriched solvent at constant temperature, (ii) raising the temperature of said enriched solvent at constant pressure, or (iii) reducing the pressure and raising the temperature of said enriched solvent.