Method for producing hollow fiber carbon membrane and separation membrane module

• US 10,456,751 B2
• Filed: 03/02/2016
• Issued: 10/29/2019
• Est. Priority Date: 03/27/2015
• Status: Active Grant

• Current Assignee: National Institute of Advanced Industrial Science and Technology (Government of Japan)
• Original Assignee: National Institute of Advanced Industrial Science and Technology (Government of Japan)
• Inventors: Yoshimune, Miki, Haraya, Kenji, Hara, Nobuo
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US15/562,150
• Publication Number:
  US 20180078907A1
• Time in Patent Office: 1,336 Days
• CPC Class Codes: B01D 2053/224 with hollow fibres
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• 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: D01D 5/24 with a hollow structure; Spinnerette packs therefor D01D5/38 takes precedence; producing tubes of plastic material B29D; addition of agents forming hollow filaments D01F1/08
• CPC Class Codes: D01F 6/76 from other polycondensation products
• CPC Class Codes: D01F 9/24 from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 70/62 related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

An object of the present invention is to provide a method capable of easily controlling the permeation rate and the selectivity of gas molecules, in a hollow fiber carbon membrane which can be used as a gas separation membrane. The present invention provides a method of producing a hollow fiber carbon membrane, the method including: a preparation step of preparing a precursor made of an organic polymer compound in the form of a hollow fiber; a preheating step of heating the precursor to a temperature of 150° C. to 400° C. in an atmosphere containing an oxygen gas; and a carbonization step of heating the precursor which has been subjected to the preheating step to a temperature of 450° C. to 850° C., thereby carbonizing the precursor; wherein the carbonization step includes heating the precursor in the presence of a hydrocarbon gas which may contain a nitrogen atom and which has from 1 to 8 carbon atoms. This method allows for easily controlling the permeation rate and the selectivity of gas molecules, in the resulting hollow fiber carbon membrane.

Claims

1. A method of producing a hollow fiber carbon membrane, the method comprising:

a preparation step of preparing a precursor made of an organic polymer compound in the form of a hollow fiber;

a preheating step of heating the precursor to a temperature of 150°

C. to 400°

C. in an atmosphere containing an oxygen gas; and

a carbonization step of heating the precursor which has been subjected to the preheating step to a temperature of 450°

C. to 850°

C., thereby carbonizing the precursor;

wherein the carbonization step comprises heating the precursor in the presence of a hydrocarbon gas which may contain a nitrogen atom and which has from 1 to 8 carbon atoms, and the hydrocarbon gas is supplied from an external source.

2. The method of producing a hollow fiber carbon membrane according to claim 1, wherein the hydrocarbon gas is a hydrocarbon containing a carbon-carbon unsaturated bond.

3. The method of producing a hollow fiber carbon membrane according to claim 1, wherein the organic polymer compound comprises at least one selected from the group consisting of polyphenylene oxide, and a polyphenylene oxide derivative containing structures represented by the following formulae (a) and (b):

4. A separation membrane module comprising a hollow fiber carbon membrane produced by the method of producing a hollow fiber carbon membrane according to claim 1.

5. The method of producing a hollow fiber carbon membrane according to claim 2, wherein the organic polymer compound comprises at least one selected from the group consisting of polyphenylene oxide, and a polyphenylene oxide derivative containing structures represented by the following formulae (a) and (b):

6. A separation membrane module comprising a hollow fiber carbon membrane produced by the method of producing a hollow fiber carbon membrane according to claim 2.

7. A separation membrane module comprising a hollow fiber carbon membrane produced by the method of producing a hollow fiber carbon membrane according to claim 3.

8. A separation membrane module comprising a hollow fiber carbon membrane produced by the method of producing a hollow fiber carbon membrane according to claim 5.

9. The method of producing a hollow fiber carbon membrane according to claim 1, wherein the carbonization step further comprises supplying an inert gas and the hydrocarbon gas simultaneously, and the concentration of the hydrocarbon gas (volume flow rate of hydrocarbon gas/volume flow rate of inert gas×

100[% by volume]) is 5% by volume or more, and 50% by volume or less.

10. The method of producing a hollow fiber carbon membrane according to claim 1, further comprising elevating a temperature within a reactor while supplying an inert gas in the absence of the hydrocarbon gas before starting the carbonization step.

11. The method of producing a hollow fiber carbon membrane according to claim 1, wherein the hydrocarbon gas has from 1 to 4 carbon atoms.

12. The method of producing a hollow fiber carbon membrane according to claim 2, wherein the carbonization step further comprises supplying an inert gas and the hydrocarbon gas simultaneously, and the concentration of the hydrocarbon gas (volume flow rate of hydrocarbon gas/volume flow rate of inert gas×

100[% by volume]) is 5% by volume or more, and 50% by volume or less.

13. The method of producing a hollow fiber carbon membrane according to claim 2, further comprising elevating a temperature within a reactor while supplying an inert gas in the absence of the hydrocarbon gas before starting the carbonization step.

14. The method of producing a hollow fiber carbon membrane according to claim 2, wherein the hydrocarbon gas has from 1 to 4 carbon atoms.

15. The method of producing a hollow fiber carbon membrane according to claim 3, wherein the carbonization step further comprises supplying an inert gas and the hydrocarbon gas simultaneously, and the concentration of the hydrocarbon gas (volume flow rate of hydrocarbon gas/volume flow rate of inert gas×

100[% by volume]) is 5% by volume or more, and 50% by volume or less.

16. The method of producing a hollow fiber carbon membrane according to claim 3, further comprising elevating a temperature within a reactor while supplying an inert gas in the absence of the hydrocarbon gas before starting the carbonization step.

17. The method of producing a hollow fiber carbon membrane according to claim 3, wherein the hydrocarbon gas has from 1 to 4 carbon atoms.

18. The method of producing a hollow fiber carbon membrane according to claim 4, wherein the carbonization step further comprises supplying an inert gas and the hydrocarbon gas simultaneously, and the concentration of the hydrocarbon gas (volume flow rate of hydrocarbon gas/volume flow rate of inert gas×

100[% by volume]) is 5% by volume or more, and 50% by volume or less.

19. The method of producing a hollow fiber carbon membrane according to claim 4, further comprising elevating a temperature within a reactor while supplying an inert gas in the absence of the hydrocarbon gas before starting the carbonization step.

20. The method of producing a hollow fiber carbon membrane according to claim 4, wherein the hydrocarbon gas has from 1 to 4 carbon atoms.