Hollow membranes with capillary tubes, fluid treatment modules that use them and methods of manufacturing them

• US 6,649,058 B1
• Filed: 03/19/2001
• Issued: 11/18/2003
• Est. Priority Date: 10/29/1997
• Status: Expired due to Fees

• Current Assignee: Commissariat a L'Energie Atomique (French Alternative Energies and Atomic Energy Commission), Nikolai Jitariouk
• Original Assignee: Commissariat a L'Energie Atomique (French Alternative Energies and Atomic Energy Commission), Nikolai Jitariouk
• Inventors: Jitariouk, Nicolaï, Le Moel, Alain
• Primary Examiner(s): Walker, W. L.
• Assistant Examiner(s): SORKIN, DAVID L
• Application Number:
  US09/810,491
• Time in Patent Office: 974 Days
• Field of Search: 216/2, 216/56, 427/244, 210/321.75, 210/321.79, 210/321.78, 210/321.8, 210/321.84, 210/321.87, 210/321.88, 210/321.89, 210/500.23, 210/500.27, 210/500.28
• US Class Current: 210/321.75
• CPC Class Codes: B01D 2313/42 Catalysts within the flow path
• CPC Class Codes: B01D 2319/04 Elements in parallel
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 63/00 Apparatus in general for separation processes using semi-permeable membranes
• CPC Class Codes: B01D 63/0231 using supporting structures, e.g. filaments for weaving mats
• CPC Class Codes: B01D 67/003 by selective elimination of components, e.g. by leaching
• CPC Class Codes: B01D 69/00 Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/72 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 35/59 Membranes
• CPC Class Codes: B01J 8/009 Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane

Abstract

The invention relates to a hollow membrane (11) comprising two support layers arranged one above the other forming a space between them and a plurality of capillary tubes arranged between the support layers forming capillary channels for the flow of a first fluid, the space between the capillary tubes forming an internal cavity for the circulation of a second fluid around the capillary tubes, and the whole assembly being made of an organic polymer.

These membranes (11) can be assembled into modules for the treatment of a fluid with intermediate porous panels (13).

Claims

1. A method of manufacturing a fluid treatment module comprising the following steps:

1) preparing at least two composite membranes by forming, on the external surfaces and in the pores of a membrane matrix comprising rectilinear open pores arranged between its two external surfaces, a coating of organic polymer by in situ polymerization of a monomer precursor of the polymer to create capillary channels within the membrane matrix,

2) forming, from the composite membranes and panels of porous material, a stack in which each composite membrane is arranged between two panels of porous material,

3) forming sealed joints between the composite membranes and the porous panels on the lateral faces of the stack,

4) making openings in the sealed joint only at the level of the composite membranes, and for each composite membrane only on two different lateral faces of the stack,

5) introducing through these openings a first reactant capable of destroying the material forming the membrane matrix of the composite membranes without affecting the polymer covering the surfaces and the pores of the membrane matrix, in order to obtain a stack of hollow membranes and panels of porous material in which the internal cavities of the hollow membranes are accessible on two lateral faces of the stack.

2. The method according to claim 1, in which the organic polymer coating and a capillary tube formed from the membrane matrix is subjected, during or after polymerization to treatment by:

a) a second reactant chosen from among the Lewis acids and from among the salts of said acids, or

b) a second reactant chosen from among the hydroxides or carbonates of alkali metals, thereby obtaining different pore sizes in the capillary channel walls, different degrees of wettability of said walls by aqueous solutions or by organic solvents, and/or different electro-conductivity properties, rigidity, porosity and/or flexibility.

3. The method according to claim 2 wherein the Lewis acid is of formula R—

SO₃H and wherein R is selected from the group consisting of alkyl, aryl, and alkylaryl.

4. The method according to claim 1, in which step 3) is carried out by causing the penetration of an adhesive into the porous panels and the composite membranes on the lateral faces of the stack.

5. The method according to claim 4, comprising, in addition, a step of treating the panels of porous material, in order to facilitate the penetration of the adhesive, before carrying out step 3).

6. The method according to claim 1 wherein the membrane matrix is made of a polymeric material or an inorganic material and in which the rectilinear pores of the membrane matrix have been created by irradiation using a beam of heavy ions, followed by dissolution of the material in the tracks formed by the ions and/or around them.

7. The method according to claim 6 wherein the polymeric material is chosen from among polycarbonates, polyethylene terephthalate, polyimides or polyvinylidene fluoride and said first reactant is chosen from among the inorganic bases and acids.

8. The method according to claim 6 wherein said inorganic material is aluminum oxide and said first reactant is chosen from among the inorganic bases and acids.

9. The method according to claim 6 wherein said inorganic material is mica and said first reactant is hydrofluoric acid.

10. The method according to claim 1 wherein the in situ polymerization of the precursor polymer monomer is carried out by chemical or electrochemical oxidation of said monomer.

11. The method according to claim 10 wherein the polymerization by chemical oxidation is carried out by bringing one face of the membrane matrix into contact with a solution of said monomer and the other face of the membrane matrix with a solution of an oxidizing agent.