Skinned, asymmetric poly(phenylene ether) co-polymer membrane; gas separation unit, and preparation method thereof

• US 10,080,996 B2
• Filed: 04/30/2015
• Issued: 09/25/2018
• Est. Priority Date: 05/01/2014
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Berzinis, Albin Peter, Halbfinger, Rachel Elizabeth, Bikel, Matias, Bajaj, Pooja
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US15/303,562
• Publication Number:
  US 20170021311A1
• Time in Patent Office: 1,244 Days
• CPC Class Codes: B01D 2053/224 with hollow fibres
• CPC Class Codes: B01D 2323/06 Specific viscosities of materials involved
• CPC Class Codes: B01D 2323/219 Specific solvent system
• CPC Class Codes: B01D 2323/22 Specific non-solvents or non-solvent system
• CPC Class Codes: B01D 2325/023 Dense layer within the membrane
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 63/021 Manufacturing thereof
• CPC Class Codes: B01D 63/08 Flat membrane modules
• CPC Class Codes: B01D 63/10 Spiral-wound membrane modules
• CPC Class Codes: B01D 67/0016 Coagulation
• CPC Class Codes: B01D 67/00165 Composition of the coagulation baths
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/06 Flat membranes
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5211 Polyethylene glycol or polyethyleneoxide
• CPC Class Codes: B01D 71/76 Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24

Abstract

An asymmetric membrane having a substantially non-porous surface layer is made by a method including: dissolving a poly(phenylene ether) copolymer in a solvent mixture including a first solvent and a second solvent to provide a membrane-forming composition; and phase-inverting the membrane forming composition in a first non-solvent to form the membrane comprising a substantially non-porous surface layer. The first solvent is a water-miscible polar aprotic solvent, and the second solvent is a polar solvent having two to eight carbon atoms.

Claims

1. An asymmetric membrane having a substantially non-porous surface layer made by a method comprising:

dissolving a poly(phenylene ether) copolymer having an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25°

C., and a weight average molecular weight of 100,000 to 500,000 daltons, measured by gel permeation chromatography against polystyrene standards, in a solvent mixture comprising a first solvent and a second solvent to provide a membrane-forming composition;

phase-inverting the membrane-forming composition in a first non-solvent to form the membrane having a substantially non-porous surface layer;

wherein the first solvent is a water-miscible polar aprotic solvent, and the second solvent is a polar solvent having two to eight carbon atoms.

2. The asymmetric membrane of claim 1, wherein the method further comprises washing the membrane in a second non-solvent and drying the membrane.

3. The asymmetric membrane of claim 1, wherein the poly(phenylene ether) copolymer comprises first and second repeat units having the structure:

4. The asymmetric membrane of claim 1, wherein the poly(phenylene ether) copolymer comprises, consists essentially of, or consists of:

80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and

20 to 80 mole percent repeat units derived from a first monohydric phenol having the structure

5. The asymmetric membrane of claim 1, in which a hydrophilic polymer is not present.

6. The asymmetric membrane of claim 5, wherein the hydrophilic polymer is poly(vinyl pyrrolidone), poly(oxazoline), poly(ethylene glycol), poly(propylene glycol), a poly(ethylene glycol) monoether or monoester, a poly(propylene glycol) monoether or monoester, a block copolymer of poly(ethylene glycol) and poly(propylene glycol), or a combination comprising at least one of the foregoing.

7. The asymmetric membrane of claim 4, wherein the first monohydric phenol is 2-methyl-6-phenylphenol.

8. The asymmetric membrane of claim 1, wherein the solubility of the poly(phenylene ether) copolymer in the water-miscible polar aprotic solvent is 50 to 400 grams per kilogram at 25°

C., based on the combined weight of the poly(phenylene ether) copolymer and the solvent.

9. The asymmetric membrane of claim 1, further comprising a poly(phenylene ether) homopolymer, polyethersulfone, polysulfone, polyphenylsulfone, or a combination comprising at least one of the foregoing.

10. A gas separation module comprising the asymmetric membrane of claim 1.

11. The gas separation module of claim 10, wherein the asymmetric membrane comprises an asymmetric hollow fiber.

12. The gas separation module of claim 11, comprising a bundle of 10 to 10,000 of the asymmetric hollow fibers.

13. The gas separation module of claim 12, comprising a plurality of the bundles.

14. The gas separation module of claim 12, wherein the gas separation module comprises:

an enclosure configured to contain the bundle, the enclosure having an outlet adapted for withdrawing a permeate fluid;

a first encasement comprising a thermoset or a thermoplastic polymeric material and located at a first end of the bundle, arranged such that the hollow fiber membranes are embedded in the first encasement and communicate through the first encasement and are open on an outer face of the first encasement;

a second encasement comprising a thermoset or a thermoplastic polymeric material and located at a second end of the bundle opposite the first end of the bundle, arranged such that the hollow fiber membranes are embedded in the second encasement and communicate through the second encasement and are open on an outer face of the second encasement;

a first end cap arranged and adapted for attaching and sealing to the first end of the bundle or enclosures at or near the first encasement;

a second end cap arranged and adapted for attaching and sealing to the second end of the bundle or enclosures at or near the second encasement;

an inlet for introducing a fluid mixture to be separated into bores of the hollow fiber membranes at the first encasement; and

an outlet for withdrawing a retentate fluid from the bores for the hollow fiber membranes at the second encasement.

15. The gas separation module of claim 10, wherein the asymmetric membrane is a form of a sheet.

16. The gas separation module of claim 10, wherein the asymmetric membrane is in a form of a spiral.

17. The gas separation module of claim 15, wherein gas separation module comprises:

a hollow core comprising perforations;

the asymmetric membrane wound around the core; and

a spacer disposed adjacent to the asymmetric membrane.

21. The asymmetric membrane of claim 1, wherein the intrinsic viscosity is 0.8 to 1.5 deciliters per gram.

18. A method of forming an asymmetric membrane having a non-porous surface layer comprising:

dissolving a poly(phenylene ether) copolymer having an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25°

C. in a solvent mixture comprising a first solvent and a second solvent to make a membrane-forming composition, wherein the first solvent is a water-miscible polar aprotic solvent, and the second solvent is a polar solvent having two to eight carbon atoms; and

phase inverting the membrane-forming composition in a first non-solvent to form the membrane.

19. The method of claim 18, further comprising washing the asymmetric membrane in a second non-solvent.

20. The method of claim 18, further comprising drying the asymmetric membrane.