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

• US 10,543,462 B2
• Filed: 12/29/2016
• Issued: 01/28/2020
• 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:
  US15/394,204
• Publication Number:
  US 20180161731A1
• Time in Patent Office: 1,125 Days
• CPC Class Codes: B01D 2053/224 with hollow fibres
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/082 Cooling
• CPC Class Codes: B01D 2323/42 Details of membrane preparation apparatus
• CPC Class Codes: B01D 2323/50 Control of the membrane preparation process
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• 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: 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 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 bundle in order to sweep away off-gases that are formed during pyrolysis.

Claims

1. A method for manufacturing a plurality of hollow fiber CMS membranes, comprising the steps of:

heating, in a pyrolysis chamber, a bundle of polymeric membranes comprising 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 having a length dimension that is greater than its width and thickness dimensions, said heating step being performed at a temperature and time duration sufficient to pyrolyze the plurality of green, polymeric hollow fiber membranes; and

directing a flow of pyrolysis gas during said heating step through said bundle in a direction perpendicular to the length direction of the bundle, 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 plurality of green, polymeric hollow fiber membranes.

2. The method of claim 1, wherein the bundle is formed by skeining a continuous length of a green, polymeric hollow fiber membrane onto two rods and cutting the skeined green, polymeric hollow fiber membrane adjacent the two rods.

3. The method of claim 1, wherein, during performance of said step of directing, the bundle is contained within a container having solid sides, a porous top, and a porous bottom.

4. The method of claim 1, wherein the bundle has a length dimension that is two to seventy times its width or diameter dimension.

5. The method of claim 1, wherein the bundle has a length dimension that is ten to thirty times its width or diameter dimension.

6. The method of claim 1, wherein the pyrolysis gas comprises 2-40 ppm of O₂ with a balance of inert gas.

7. The method of claim 1, wherein the pyrolysis gas essentially consists of an inert gas with substantially no O₂.

8. The method of claim 1, wherein the bundle is heated in the pyrolysis chamber up to a temperature from 500-1,000°

C.

9. The method of claim 1, wherein the bundle is heated in the pyrolysis chamber up to a temperature from 450-800°

C.

10. The method of claim 1, wherein the bundle has a length dimension that is ten to thirty times its width or diameter dimension and the bundle is heated in the pyrolysis chamber up to a temperature from 450-800°

C.

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

heating, in a pyrolysis chamber, a bundle of polymeric membranes comprising 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 having a length dimension that is greater than its width and thickness dimensions, said heating step being performed at a temperature and time duration sufficient to pyrolyze the plurality of green, polymeric hollow fiber membranes; and

directing a flow of pyrolysis gas during said heating step across said bundle in a direction perpendicular to the length direction of the bundle, 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 plurality of green, polymeric, hollow fiber membranes;

forming one or more tubesheets on a bundle of hollow fiber CMS membranes resulting from said steps of heating and directing; and

following said forming step, placing the bundle of hollow fiber CMS membranes inside a pressure vessel having a feed port, a permeate port, and a non-permeate port.