Hollow fiber membrane and braided tubular support therefor

• US 6,354,444 B1
• Filed: 06/17/1999
• Issued: 03/12/2002
• Est. Priority Date: 07/01/1997
• Status: Expired due to Term

• Current Assignee: Zenon Technology Partnership
• Original Assignee: Zenon Environmental Incorporated (Veolia Environnement SA)
• Inventors: Goodboy, Kenneth Paul, Mahendran, Mailvaganam, Fabbricino, Luigi
• Primary Examiner(s): Fortuna, Ana
• Assistant Examiner(s): Ward, Richard W.
• Application Number:
  US09/335,073
• Time in Patent Office: 999 Days
• Field of Search: 428/36.3, 87/9, 210/490, 210/497.1, 210/500.27, 210/500.23, 210/500.42, 210/500.25, 555/20, 555/27
• US Class Current: 210/490
• CPC Class Codes: B01D 2325/0233 with clearly distinguishable layers
• CPC Class Codes: B01D 2325/04 Characteristic thickness
• CPC Class Codes: B01D 2325/40 Fibre reinforced membranes
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/1071 Woven, non-woven or net mesh
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 69/1411 containing dispersed material in a continuous matrix
• CPC Class Codes: B01D 71/34 Polyvinylidene fluoride
• CPC Class Codes: C08K 9/02 Ingredients treated with inorganic substances
• CPC Class Codes: C08L 27/16 Homopolymers or copolymers or vinylidene fluoride

Abstract

An asymmetric membrane comprising a tubular polymer film in combination with a tubular braid on which the film is supported, requires the braid be macroporous and flexible, yet sufficiently strong to withstand continuous flexing, stretching and abrasion during use for microfiltration (MF) or ultrafiltration (UF). The specifications for a braid of a long-lived membrane are provided. A membrane is formed by supporting a polymer film in which particles of calcined α-alumina are dispersed, on the defined tubular braid.

Claims

1. An outside-in hollow fiber asymmetric membrane comprising a flexible macroporous tubular braid support having a tubular film of synthetic resinous material supported on the outer circumferential surface of the braid without the support being embedded in the film which has a wall thickness of less than 0.2 mm, the braid comprising, from about 16 to 60 separate yarns, each on its own carrier, each yarn using multifilament 150 to 500 denier (gm/9000 meters) yarn, each multifilament being made with from 25 to 750 filaments, each filament being from 0.5 to 7 denier, the braid being woven with from 1 to 3 multifilament ends at from 30 to 45 picks (crosses/inch), with a wall thickness in the range from about 0.2 mm but less than three times the diameter of the yarn from which said braid is woven, the braid having a stable heat-pre-shrunk length which is in the range from about 1% to 20% less than its unshrunk length, an air permeability in the range from about 1 to about 10 cc/sec/cm² at 1.378 kPa, and extension at break of the pre-shrunk braid is at least 10%,

such that the membrane is adapted for use as a microfiltration or ultrafiltration liquid separation membrane.

2. The asymmetric membrane of claim 1 wherein said ends are non-plied in each said yarn but lie linearly adjacent each other until taken up to form said braid which is pre-shrunk to a length in the range from about 1% to 8% less than its unshrunk length.

3. The asymmetric membrane of claim 1 wherein the tubular braid support has a cylindricity greater than 0.8 and a maximum extension at break of at least 10%.

4. The asymmetric membrane of claim 3 wherein the tubular braid support has a wall thickness in the range from about 0.2 mm to less than three times the diameter of said yarn, and a maximum extension at break of at least 20%.

5. The asymmetric membrane of claim 3 wherein the tubular braid support has separate yarns woven in a pattern chosen from Regular, Diamond and Hercules.

6. In an outside-in hollow fiber asymmetric semipermeable membrane comprising,

(i) a macroporous foraminous tubular support means having an outer surface;

and,

(ii) a polymeric film of a reaction product of (a) a complex of polyvinylidene difluoride (PVDF) with calcined α

-alumina particles, and (b) a hydrophilic polymer adapted to impart hydrophilicity to said membrane;

said particles having a primary particle size in the range from about 0.1 μ

m to 5 μ

m being present in an amount at least 1 percent by weight, but less than 50 percent by weight, of said film;

said film being supported by said outer surface, and said film having a peripheral barrier layer or “

skin”

integral with successive microporous layers having pores having an average diameter in the range from about 0.01 μ

m to about 0.3 μ

m, in open communication with each other,

the improvement comprising,

a flexible macroporous tubular braid support comprising from about 16 to 60 separate yarns, each on its own carrier, each yarn using multifilament 150 to 500 denier (gm/9000 meters) yarn, each multifilament being made with from 25 to 750 filaments, each filament being from 0.5 to 7 denier, said braid being woven with from 1 to 3 multifilament ends at from 30 to 45 picks (crosses/inch), and said braid has a wall thickness in the range from about 0.2 mm but less than three times the diameter of the yarn from which said braid is woven, has a stable heat-pre-shrunk length which is in the range from about 1% to 20% less than its unshrunk length, and an air permeability in the range from about 2.67 to about 7.09 cc/sec/cm² at 1.378 kPa,

whereby said membrane is adapted for use as a microfiltration or ultrafiltration liquid separation membrane.

7. The hollow fiber of claim 6 wherein said macroporous foraminous tubular support means support means has a stable heat-pre-shrunk length which is in the range from about 1% to 20% less than its unshrunk length and an air permeability less than 10 cc/sec/cm² at 1.378 kPa.

8. The hollow fiber of claim 7 wherein said filaments are formed from a synthetic resin selected from the group consisting of polyester and polyamide.

9. The hollow fiber of claim 8 wherein said braid has an inside diameter more than 0.5 mm, an outside diameter less than 3 mm and a wall thickness in the range from about 0.2 mm to about 1.0 mm.

10. The tubular braid support of claim 9 wherein said separate yarns are woven in a pattern chosen from Regular, Diamond and Hercules.

11. The hollow fiber of claim 7 wherein said braid, stretched longitudinally, has an extension at break in the range from 10% to 30%.