High flux semipermeable membranes

• US 4,950,404 A
• Filed: 08/30/1989
• Issued: 08/21/1990
• Est. Priority Date: 08/30/1989
• Status: Expired due to Term

• Current Assignee: Koch Membrane Systems, Inc. (KOCH Industries Incorporated)
• Original Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Inventors: Chau, Michael M.
• Primary Examiner(s): Sever, Frank
• Application Number:
  US07/400,440
• Time in Patent Office: 356 Days
• Field of Search: 210/490, 210/500.38, 210/500.37, 210/500.39, 210/500.41, 210/653, 210/654, 264/41, 264/45.1, 264/45.5, 264/48, 264/DIG. 48, 264/DIG. 62
• US Class Current: 210/500.27
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction

Abstract

High flux semipermeable membranes which comprise a polymerized reaction product within and/or on a porous support may be prepared by contacting the porous support such as a polysulfone sheet with an aqueous solution of an polyamine, said aqueous solution containing a polar aprotic solvent not reactive with amines and optionally an acid acceptor. The surface of the coated support is dried to the touch and then contacted with an organic solution of an polycarboxylic acid halide for a period of time sufficient to form a polymerized reaction product within and/or on the surface of the support material. The resulting composite may be post treated by washing with an alkaline compound. The resultant membrane composite may be used in separation processes such as the desalination of brackish or seawater, or the softening of domestic hard water.

Claims

1. A semipermeable membrane having properties for providing increased flux while retaining salt rejection and chlorine resistance prepared by coating a porous support with an aqueous solution of an polyamine or bisphenol which contains a polar aprotic solvent not reactive with amines having properties for dissolving or plasticizing said support, removing excess of said solution, contacting the coated porous support with an organic solvent solution of an polyacyl halide, polysulfonyl halide, or polyisocyanate to form a reaction product within and/or on the surface of said porous support, and curing the resultant composite at curing conditions to form said high flux semipermeable membrane.

2. The high flux membrane of claim 1 further characterized in that the surfaces of the coated support are air dried before contacting one of said surfaces with said organic solvent solution.

3. The high flux membrane of claim 1 wherein said aqueous solution contains a polyamine.

4. The high flux membrane of claim 3 in which said polyamine is an aromatic amine.

5. The high flux membrane of claim 4 wherein said aromatic polyamine is at least one member of the group consisting of m-phenylenediamine, o-phenylenediamine, p-penylenediamine, of m-phenylenediamine, o-phenylenediamine, p-phenlenediamine, 4-chlorophenylenediamine, and 5-chlorophenylenediamine.

6. The high flux membrane of claim 1 in which said polyacyl halide is an aromatic polycarboxylic acid halide.

7. The high flux membrane of claim 6 wherein said aromatic acid halide is at least one member of the group consisting of isophthaloyl chloride, trimesoyl chloride, trimellitoyl chloride and terephthaloyl chloride.

8. The high flux membrane of claim 1 in which said polar aprotic solvent is at least one member of the group consisting of N-methylpyrrolidone, 2-pyrrolidones, N,N-dimethylformamide, dioxane, pyridine, lutidines, picolines, tetrahydrofuran, sulfolane, sulfolene, hexamethylphosphoramide, triethylphosphite, N,N-dimethylacetamide, and N,N-dimethylpropionamide.

9. The high flux membrane of claim 8 in which said solvent is N-methylpyrrolidone.

10. The high flux membrane of claim 8 wherein the concentration of said solvent in said aqueous solution is about 0.01 to 75 wt. %.

11. The high flux membrane of claim 10 wherein the concentration of said solvent is 0.1 to 20 wt. %.

12. The high flux membrane of claim 11 wherein the concentration of said solvent is 1 to 20 wt. %.

13. The high flux membrane of claim 1 further characterized in that said aqueous solution contains an acid acceptor.

14. The high flux membrane of claim 1 in which the pH of said aqueous solution is in a range of from about 8 to about 14.

15. The high flux membrane of claim 1 in which the aqueous solution contains a polyamine in a concentration of about 0.1% to about 20% by weight and said organic solution contains a polyacyl halide in a concentration of about 0.01% to about 10% by weight.

16. The high flux membrane of claim 1 in which said curing conditions include a temperature in the range of from about 20°

to about 150°

C for a period of time in the range of from about 1 second to about 2 hours.

17. The high flux membrane of claim 1 further characterized in that said membrane is subjected to treatment with an alkaline compound.

18. The high flux membrane of claim 17 in which the cured membrane is washed at a temperature is in a range of from about 20°

C to about 100°

C.

19. A process comprising;

preparing a semipermeable membrane providing increased flux while retaining salt rejection and chlorine resistance by coating on a porous support an aqueous solution of an aromatic polyamine which contains a polar aprotic solvent not reactive with amines having properties for dissolving or plasticizing said support and optionally an acid acceptor, removing excess solution, drying the surface of the coated support, contacting the dried surface of the coated support with an organic solution of an aromatic polycarboxylic acid halide to form a reaction product within and/or on the surface of said porous support and curing the resultant composite at curing conditions.

20. The process of claim 19 further comprising the steps of washing the cured membrane with an alkaline compound at an elevated temperature and pH, and recovering the resultant high flux semipermeable membrane.