Hollow fiber carbon molecular sieve membranes and method of manufacturing using radial-flow pyrolysis

• US 10,549,244 B2
• Filed: 12/14/2016
• Issued: 02/04/2020
• Est. Priority Date: 12/14/2016
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Coignet, Philippe A., Kratzer, Dean W., Swaidan, Raja
• Primary Examiner(s): Yi, Stella K
• Application Number:
  US15/378,233
• Publication Number:
  US 20180161736A1
• Time in Patent Office: 1,147 Days
• CPC Class Codes: B01D 2053/224 with hollow fibres
• CPC Class Codes: B01D 2256/10 Nitrogen
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2313/23 Specific membrane protectors, e.g. sleeves or screens
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/082 Cooling
• CPC Class Codes: B01D 2325/20 Specific permeability or cut-off range
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 63/021 Manufacturing thereof
• CPC Class Codes: B01D 63/0232 using hollow fibers mats as precursor, e.g. wound or pleated mats
• CPC Class Codes: B01D 63/0233 forming the bundle
• CPC Class Codes: B01D 67/0067 by carbonisation or pyrolysis
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: B01D 71/028 Molecular sieves carbon B01D71/021
• CPC Class Codes: B01D 71/0281 Zeolites
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

One or more polymeric hollow fiber membranes are pyrolyzed to form one or more hollow fiber CMS membranes by directing a flow of pyrolysis gas through a polymeric membrane cartridge (including a porous center tube around which one or more green, polymeric, hollow fiber membranes is arranged) or a bundle of polymeric membranes (including a plurality of green, polymeric hollow fiber membranes oriented so that their ends are disposed with ends of the bundle) in a direction perpendicular to a length direction of the cartridge or bundle in order to sweep away off-gases that are formed during pyrolysis.

Claims

1. A method for manufacturing at least one hollow fiber CMS membrane, comprising the steps of:

heating, in a pyrolysis chamber, a polymeric membrane cartridge or a bundle of polymeric membranes, wherein;

the polymeric membrane cartridge comprises a porous center tube around which one or more green polymeric hollow fiber membranes is arranged,

the polymeric membrane cartridge has a length dimension that is greater than its width, thickness, and radius dimensions,

the bundle of polymeric membranes comprises a plurality of green polymeric hollow fiber membranes oriented so that first and second ends of the plurality of green polymeric hollow fiber membranes are disposed at first and second ends of the bundle,

the bundle of polymeric membranes has a length dimension that is greater than its width and thickness dimensions,

the porous center tube has at least one open end and apertures extending through a wall thickness of the porous center tube, and

said heating step is performed at a temperature and time duration sufficient to pyrolyze the one or more green polymeric hollow fiber membranes; and

directing a flow of pyrolysis gas during said heating step through said polymeric membrane cartridge or said bundle of polymeric membranes in a direction perpendicular to the length direction of the polymeric membrane cartridge or said bundle of polymeric membranes, wherein performance of said heating step results in production of pyrolysis off-gases and said flow of pyrolysis gas sweeps the pyrolysis off-gases away from the one or more green polymeric hollow fiber membrane(s).

2. The method of claim 1, wherein said heating step comprises heating, in a pyrolysis chamber, a polymeric membrane cartridge.

3. The method of claim 2, wherein the pyrolysis gas does not flow through the polymeric membrane cartridge in a direction parallel to an axis of the porous center tube.

4. The method of claim 2, wherein the polymeric membrane cartridge is contained within an outer shell having an axis coextensive with an axis of the porous center tube.

5. The method of claim 4, wherein the pyrolysis gas is introduced into an interior of the porous center tube from the at least one open end, flows outwardly in a radial direction past the one or more green polymeric hollow fiber membranes via the apertures, and is withdrawn, along with the swept pyrolysis off-gases, from a space between the bundle of polymeric membranes and the outer shell.

6. The method of claim 5, wherein the space between the bundle of polymeric membranes and the outer shell is swept with an axial flow of a sweep gas in order to enhance removal of the pyrolysis gas and swept pyrolysis off-gases therefrom.

7. The method of claim 5, wherein a vacuum is applied to the space between the bundle of polymeric membranes and the outer shell in order to enhance removal of the pyrolysis gas and swept pyrolysis off-gases therefrom.

8. The method of claim 5, wherein a porous sleeve surrounds the bundle of polymeric membranes, and along with the swept off-gases, the radial flow of pyrolysis gas travels through apertures formed in the porous sleeve.

9. The method of claim 8, wherein the porous sleeve is comprised of a metal, a carbon fiber material, or a polymeric material, the polymeric material having a melting, softening, or pyrolysis temperature higher than that achieved during said heat step.

10. The method of claim 4, wherein the pyrolysis gas is introduced into a space between the bundle of polymeric membranes and the outer shell, and along with the swept off-gases, flows inwardly in the radial direction past the one or more green polymeric hollow fiber membranes through the apertures of the porous center tube and into an interior of the porous center tube where they are withdrawn therefrom.

11. The method of claim 10, wherein the interior of the porous center tube is swept with an axial flow of a sweep gas in order to enhance removal of the pyrolysis gas and swept pyrolysis off-gases therefrom.

12. The method of claim 10, wherein a vacuum is applied to the interior of the porous center tube in order to enhance removal of the pyrolysis gas and swept pyrolysis off-gases therefrom.

13. The method of claim 10, wherein a porous sleeve surrounds the bundle of polymeric membranes and the radial flow of pyrolysis gas travels through apertures formed in the porous sleeve.

14. The method of claim 13, wherein the porous sleeve is comprised of a metal, a carbon fiber material, or a polymeric material, the polymeric material having a melting, softening, or pyrolysis temperature higher than that achieved during said heat step.

15. The method of claim 2, wherein the porous center tube is comprised of a metal.

16. The method of claim 15, wherein the porous center tube is comprised of a sintered metal.

17. The method of claim 2, where said at least one green polymeric hollow fiber membrane is wound around the porous center tube.

18. The method of claim 2, wherein said polymeric membrane cartridge includes more than 1,000 green polymeric hollow fiber membranes, each one of which extends in a direction parallel to a porous center tube axis.

19. The method of claim 1, wherein:

said heating step comprises heating, in a pyrolysis chamber, a bundle of polymeric membranes; and

the flow of pyrolysis gas is directed across a thickness dimension of the bundle of polymeric membranes.

20. A method of manufacturing a hollow fiber CMS membrane module, comprising the steps of:

heating, in a pyrolysis chamber, a polymeric membrane cartridge, wherein;

the polymeric membrane cartridge comprises a porous center tube around which one or more green polymeric hollow fiber membranes is arranged,

the polymeric membrane cartridge has a length dimension that is greater than its width, thickness, and radius dimensions,

the porous center tube has at least one open end and apertures extending through a wall thickness of the porous center tube, and

said heating step is performed at a temperature and time duration sufficient to pyrolyze the one or more green polymeric hollow fiber membranes; and

directing a flow of pyrolysis gas during said heating step through the one or more green;

polymeric hollow fiber membranes in either an outwardly radial direction from an interior of the porous center tube or in an inwardly radial direction toward the interior of the porous center tube, wherein performance of said heating step results in production of pyrolysis off-gases and said radial flow pyrolysis gas sweeps the pyrolysis off-gases away from the one or more green polymeric hollow fiber membranes;

forming one or more tubesheets on a CMS membrane cartridge resulting from said steps of heating and directing;

following said forming step, placing the CMS membrane cartridge inside a pressure vessel having a feed port, a permeate port, and a non-permeate port, wherein the porous center tube is in fluid communication with either the permeate port, the non-permeate port, or the feed gas port.