Process for fluid/dense gas extraction under enhanced solubility conditions

• US 5,932,101 A
• Filed: 08/14/1997
• Issued: 08/03/1999
• Est. Priority Date: 08/29/1996
• Status: Expired due to Fees

• Current Assignee: North Carolina State University (University of North Carolina System), University of North Carolina At Chapel Hill (University of North Carolina System)
• Original Assignee: Eastman Chemical Company
• Inventors: Kanel, Jeffrey Scott, Marentis, Rodger Thomas
• Primary Examiner(s): KIM, SUN U
• Application Number:
  US08/911,574
• Time in Patent Office: 719 Days
• Field of Search: 210/634, 210/638, 210/639, 210/642, 210/643, 210/656, 426/425, 426/429, 203/19
• US Class Current: 210/634
• CPC Class Codes: B01D 11/0203 with a supercritical fluid
• CPC Class Codes: B01D 11/0407 the supercritical fluid acting as solvent for the solute

Abstract

A liquid/dense gas extraction column process providing intimate contact between a dense gas and a fluid feed containing a solute and operating in an enhanced solubility region provides solubility of a solute in the dense gas to be at least 250% by weight greater than the solubility of the solute in the dense gas at the same operating temperature and 200 bar pressure. The enhanced solubility region for carbon dioxide is a pressure range of between 450 and 1200 bar in combination with a temperature range between 50 and 300° C. The column has a diameter greater than about 3.5 centimeters and a height to diameter ratio greater than about 5.

Claims

1. A continuous liquid-dense gas extraction process comprising the steps of:

a. supplying an extraction solvent comprising a dense gas to an extraction column, wherein the extraction column has a diameter greater than about 3.5 centimeters and a height to diameter ratio greater than about 5 and operates in an enhanced solubility region having a pressure of between 450 and 1200 bar and at a temperature between 50 and 300°

C.;

b. supplying a fluid feed comprising at least one solute and a carrier fluid to the extraction column, wherein the fluid feed and the extraction solvent are supplied to the extraction column with a countercurrent flow and are intimately contacting one another a sufficient amount of time to extract the at least one solute from the carrier fluid to the extraction solvent;

the carrier fluid comprises at least one component being barely soluable in the extraction solvent and is substantially immiscible with the extraction solvent so as to provide two phases, and the at least one solute is selective to the extraction solvent with respect to the carrier fluid;

c. removing from the extraction column a raffinate comprising the carrier fluid; and

d. removing from the extraction column an extract comprising the extraction solvent and the at least one solute;

whereby the combination of pressure and temperature is sufficient for the solubility of the at least one solute in the extraction solvent to be at least 250% by weight greater than the solubility of the at least one solute in the extraction solvent at the same operating temperature and 200 bar pressure.

2. The process of claim 1 further comprising the step of separating the solute from the extraction solvent.

3. The process of claim 2 wherein the separation occurs isobarically relative to the extraction column.

4. The process of claim 2 wherein the solute is separated from the extraction solvent in a phase separation device selected from the group consisting of a decanter, a coalescer, a cyclone and a second extraction column.

5. The process of claim 4 wherein the second extraction column operates isobarically and at a lower temperature relative to the first extraction column.

6. The process of claim 1 wherein the extraction solvent is supplied to a bottom of the extraction column, the fluid feed is supplied to a top of the extraction column, the extract is removed from the top of the extraction column, and the raffinate is removed from the bottom of the extraction column.

7. The process of claim 1 wherein the extraction column operates at a pressure between above 500 and 1200 bar.

8. The process of claim 7 wherein the extraction column operates at a pressure between above 700 and 1200 bar.

9. The process of claim 1 wherein the extraction column operates at a temperature between 80 and 250°

C.

10. The process of claim 1 wherein the extraction column has a diameter between 5 and 300 centimeters and a height to diameter ratio between 10 and 200.

11. The process of claim 10 wherein diameter of the extraction column is between 5 and 100 centimeters.

12. The process of claim 1 wherein the dense gas is supercritical carbon dioxide.

13. The process of claim 1 wherein the fluid feed is a solution, a dispersion, a slurry or combination thereof.

14. The process of claim 1 wherein the carrier fluid substantially comprises water, a polymer or a low-volatility high-molecular weight hydrocarbon.

15. The process of claim 1 wherein the fluid feed is a fermentation broth and the solute is a product of the fermentation broth.

16. The process of claim 15 wherein the product of the fermentation broth is selected from the group consisting of ethanol, carotenoids, tocopherols, tocotrienols, 2-keto-gulonic acid, and ascorbic acid.

17. The process of claim 1 wherein the solute is an alkaloid.

18. The process of claim 17 wherein the alkaloid is selected from the group consisting of caffeine, nicotine, theobromine, or combinations thereof.

19. The process of claim 1 wherein the solute is derived from plant matter, animal matter or microorganisms.

20. The process of claim 1 wherein the solute forms an azeotropic mixture with the carrier fluid.

21. The process of claim 1 wherein the selectivity of the solute for the extraction solvent is greater than unity with respect to the carrier fluid.

22. The process of claim 1 wherein the extraction solvent further comprises a co-solvent and the extract further comprises the co-solvent, the solute being selective to the extraction solvent and the co-solvent with respect to the carrier fluid.

23. The process of claim 22 wherein the co-solvent and the solute react with each other.

24. The process of claim 22 wherein the co-solvent is selected from the group consisting of benzene, toluene, xylene, acetonitrile, acetone, methylene chloride, cyclohexane, hexane, n-heptane, methyl cyclohexane, iso-octane, octane, nonane, decane, ethyl acetate, ethanol, methanol, phase transfer catalyst, amines, chelating agents and mixtures thereof.

25. The process of claim 1 wherein the fluid feed further comprises a co-solvent and the extract further comprises the co-solvent, the solute being selective to the co-solvent with respect to the carrier fluid.

26. The process of claim 25 wherein the co-solvent is selected from the group consisting of benzene, toluene, xylene, acetonitrile, acetone, methylene chloride, cyclohexane, hexane, n-heptane, methyl cyclohexane, iso-octane, octane, nonane, decane, ethyl acetate, ethanol, methanol, phase transfer catalyst, amines and chelating agents and mixtures thereof.

27. The process of claim 1 wherein the extraction solvent further comprises a second solute, the second solute being selective to the carrier fluid with respect to the dense gas and the raffinate further comprises the second solute.

28. The process of claim 1 further comprising the step of applying a thermal gradient across the length of the extraction column wherein the extraction of a second solute from the fluid feed to the extraction solvent is suppressed.

29. A continuous extraction process comprising the step of countercurrently and intimately contacting a fluid feed comprising at least one solute and a carrier fluid with supercritical carbon dioxide in an extraction column a sufficient amount of time to extract the at least one solute from the carrier fluid to the supercritical carbon dioxide, wherein the carrier fluid comprises substantially water, the at least one solute is selective to the supercritical carbon dioxide with respect to the carrier fluid, and the extraction column operates in an enhanced solubility region at a pressure of between 600 and 850 bar and at a temperature between 80 and 250°

C. and has a diameter greater than about 3.5 centimeters and a height to diameter ratio greater than about 5;

whereby the combination of pressure and temperature is sufficient for the solubility of the at least one solute in the supercritical carbon dioxide to be at least 250% by weight greater than the solubility of the at least one solute in the supercritical carbon dioxide at the same operating temperature and 200 bar pressure.

30. The process of claim 29 wherein the separating occurs in a phase separation device selected from the group consisting of a decanter, a coalescer, a cyclone and a second extraction column.

31. The process of claim 29 wherein the extraction column has a diameter between 5 and 300 centimeters and a height to diameter ratio between 10 and 200.

32. The process of claim 29 wherein the diameter of the extraction column is between 5 and 100 centimeters.