Supercritical separation process for complex organic mixtures

• US 4,964,995 A
• Filed: 06/16/1989
• Issued: 10/23/1990
• Est. Priority Date: 06/16/1989
• Status: Expired due to Fees

• Current Assignee: Hydrocarbon Research Incorporated
• Original Assignee: Midwest Research Institute
• Inventors: Filardo, Giuseppe, Chum, Helena L.
• Primary Examiner(s): Therkorn, Ernest G.
• Application Number:
  US07/368,170
• Time in Patent Office: 494 Days
• Field of Search: 210/634, 210/639, 210/928, 162/14, 162/16, 203/16, 203/26, 203/49
• US Class Current: 210/634
• CPC Class Codes: B01D 11/0407 the supercritical fluid acting as solvent for the solute
• CPC Class Codes: C02F 1/26 by extraction
• CPC Class Codes: C02F 11/086 in the supercritical state
• CPC Class Codes: Y10S 210/928 Paper mill waste, e.g. white water, black liquor treated

Abstract

A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70° C. and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution.

Claims

1. A process for separating low molecular weight components having a molecular weight in the range of 150 to 400, from complex aqueous organic mixtures comprising:

preparing a separation solution of supercritical carbon dioxide with an effective amount of a low boiling point entrainer selected from the group consisting of methanol, ethanol, acetone, methylethylketone, tetrahydrofuran and methyl-t-butyl ether to modify the solvation power of said supercritical carbon dioxide and extract preselected low molecular weight components;

maintaining said separation solution at a temperature of at least about 70°

C. and a pressure of at least about 1500 psi;

contacting said separation solution with said organic mixtures while maintaining said temperature and pressure until the mixtures and solution reach equilibrium to extract said preselected low molecular weight components from said organic mixtures; and

isolating the entrainer/extracted components portion from said separation solution by reducing the pressure, lowering the temperature, or a combination of reducing the pressure and lowering the temperature.

2. The process as claimed in claim 1, wherein said temperature ranges from 70°

-150°

C., and said pressure ranges from 1,500-4,000 psi.

3. The process as claimed in claim 1, wherein said entrainer includes active hydroxy groups in the presence of water to selectively extract polyhydroxy carboxylic acid or amino acids from said complex organic mixtures.

4. The process as claimed in claim 3, wherein said polyhydroxy compounds include polyhydroxycarboxylic acids.

5. The process as claimed in claim 1, wherein said entrainer comprises an effective amount of methanol and water to selectively extract polar compounds having active -COOH, -OH or -NH₂ groups.

6. The process as claimed in claim 1, wherein said effective amount of entrainer in said separation solution comprises 2-30% by weight.

7. The process as claimed in claim 1, wherein said low molecular weight components which are separated from said complex organic mixture comprise 150-400 molecular weight.

8. The process as claimed in claim 1, wherein said complex organic mixtures from which said low molecular weight components are separated are selected from the group consisting of black liquor solutions derived from alkaline wood pulping processes, pulp working solutions from the manufacturing of chemically pure cellulose, and cheese manufacturing waste streams.

9. The process as claimed in claim 8, wherein said complex organic mixtures from which said low molecular weight components are separated include phenols, carboxylic acids, and complex carbohydrates, and wherein said low molecular weight components include hydroxycarboxylic acids and substituted phenols.

10. The process as claimed in claim 1, wherein the entrainer/extracted components portion is isolated by reducing the pressure of the equilibrium solution thereby creating suspended fragments therein.

11. The process as claimed in claim 10, wherein said isolation further includes filtering the suspension and recovering the entrainer.

12. The process as claimed in claim 10, wherein said isolation includes stripping off the volatile entrainer solution to leave the extracted components.

13. The process as claimed in claim 1, wherein said preselected low molecular weight components are progressively separated in accordance with their molecular weight from said complex organic mixtures by progressively changing the entrainer concentration in the supercritical carbon dioxide/entrainer separation solution.

14. The process as claimed in claim 13, wherein low molecular weight lignin compounds are separated from said complex organic mixture by utilizing a low entrainer concentration in said separation solution, and wherein the entrainer concentration is increased to shift the extraction and separation to separating carboxylic acids from the lignin-containing complex organic mixtures.

15. The process as claimed in claim 14, wherein said entrainer includes active hydroxy groups to extract polyhydroxylated carboxylic acids.

16. The process as claimed in claim 13, wherein said entrainer comprises an alcohol, and wherein said alcohol concentration is selectively varied from 2% to 30% depending on the desired selected low molecular weight extraction component.

17. The process as claimed in claim 16, wherein said alcohol entrainer concentration is in the range of about 2-5% by weight to selectively extract low molecular weight phenolics.

18. The process as claimed in claim 16, wherein said alcohol entrainer concentration is in the range of about 10-12 weight percent to selectively extract hydroxy acids.

19. The process as claimed in claim 16, wherein said alcohol entrainer concentration is in the range of about 20-30% by weight to selectively extract complex polyhydroxy acids and amino acids.

20. The process as claimed in claim 1, wherein said preselected low molecular weight components are separated in accordance with their molecular weight from said complex organic mixtures by selectively changing the entrainer composition of the supercritical carbon dioxide/entrainer solution.

21. A process for extracting low molecular weight components having a molecular weight in the range of 150 to 400, from complex polyhydroxycarboxylic acid mixtures derived from biomass processing streams, said process comprising:

admixing a solution of supercritical carbon dioxide and an effective amount of a low boiling point organic entrainer selected from the group consisting of methanol, ethanol, acetone, methylethylketone, tetrahydrofuran and methyl-t-butyl ether to modify the solvation power of said supercritical carbon dioxide and extract preselected low molecular weight components;

maintaining said carbon dioxide solution at a temperature of about 70°

-150°

C. and a pressure of 1500-4000 psi, said carbon dioxide remaining at or about its supercritical level during the extraction phase;

contacting said carbon dioxide/entrainer solution with said polyhydroxy-carboxylic acid mixtures while maintaining said temperature and pressure until said solution is in equilibrium with said mixtures to extract said preselected low molecular weight components from said mixtures; and

isolating the entrainer/extracted components from said solution by reducing the pressure, lowering the temperature, or a combination of reducing the pressure and lowering the temperature.

22. The process as claimed in claim 21, wherein said entrainer includes hydroxy groups to extract low molecular weight polyhydroxy carboxylic acid compounds.

23. The process as claimed in claim 21, wherein said effective amount of entrainer in said carbon dioxide/entrainer solution comprises 2-30% by weight depending on the preselected component desired to be extracted.

24. The process as claimed in claim 23, wherein the preselected component being extracted may be varied by varying the concentration and/or composition of said entrainer in the supercritical carbon dioxide/entrainer solution.

25. The process as claimed in claim 21, wherein the entrainer/extracted components composition is isolated by reducing the pressure of the equilibrium solution to about 800 psi or above.

26. The process as claimed in claim 21, wherein the entrainer/extracted components composition is isolated by reducing the temperature of the equilibrium solution by 30°

-50°

C.

27. A process for separating preselected low molecular weight lignin fragments, having a molecular weight in the range of 150 to 400, from soluble lignin-containing mixtures and complex polyhydroxycarboxylic acid comprising:

preparing a solution of supercritical carbon dioxide and an effective amount of a low boiling point organic entrainer selected from the group consisting of methanol, ethanol, acetone, methylethylketone, tetrahydrofuran and methyl-t-butyl ether at a temperature of about 70°

-150°

C. and at a pressure of about 1500-4000 psi to maintain the carbon dioxide solution at or above its supercritical level and selectively extract the desired fragments;

contacting the carbon dioxide/entrainer solution with the lignin-containing mixture until the solution and mixture are in equilibrium to extract the preselected low molecular weight fragments from the mixture; and

isolating the entrainer/extracted fragments from the solution, by reducing the pressure, lowering the temperature, or a combination of reducing the pressure and lowering the temperature.

28. The process as claimed in claim 27, wherein said lignin-containing mixture comprises a black liquor mixture derived from alkaline wood pulping processes.

29. The process as claimed in claim 28, wherein said entrainer includes hydroxy groups in order to extract polyhydroxy carboxylic acid compounds from the black liquor mixtures.

30. The process as claimed in claim 29, wherein said effective amount of entrainer in said supercritical carbon dioxide/entrainer solution comprises approximately 2-30% by weight depending on the low molecular weight fragment desired to be extracted.

31. The process as claimed in claim 30, wherein the extracted component varies from low molecular weight lignin compounds to carboxylic acids as said entrainer concentration is increased in the supercritical carbon dioxide/entrainer solution.

32. The process as claimed in claim 27, wherein the entrainer/extracted fragments solution is isolated by reducing the pressure or the temperature of the mixture and solution in equilibrium.

33. The process as claimed in claim 32, wherein the entrainer/extracted fragments solution is isolated by reducing the pressure of the solution/mixture to approximately 800 psi or higher after the solution and mixture have reached equilibrium and the desired preselected fragments have been extracted from the mixture.

34. The process as claimed in claim 32, wherein the entrainer/extracted fragments solution is isolated by reducing the temperature of the solution/mixture by 30°

-50°

C. after the solution and mixture have reached equilibrium and the desired preselected fragments have been extracted from the mixture.