Process for producing carbon membranes

• US 8,608,828 B2
• Filed: 09/30/2011
• Issued: 12/17/2013
• Est. Priority Date: 10/01/2010
• Status: Expired due to Fees

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Voss, Hartwig, Therre, Joerg, Kaltenborn, Nadine, Richter, Hannes, Voigt, Ingolf
• Primary Examiner(s): Greene, Jason M
• Assistant Examiner(s): SHUMATE, ANTHONY R
• Application Number:
  US13/250,232
• Publication Number:
  US 20120079944A1
• Time in Patent Office: 809 Days
• Field of Search: 95/43, 95/45, 96/4, 96/11, 96/12
• US Class Current: 95/45
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/24 Hydrocarbons
• CPC Class Codes: B01D 2257/108 Hydrogen
• CPC Class Codes: B01D 2257/11 Noble gases
• CPC Class Codes: B01D 2257/406 Ammonia
• CPC Class Codes: B01D 2257/7022 Aliphatic hydrocarbons
• CPC Class Codes: B01D 2257/7025 Methane
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0048 by sol-gel transition
• CPC Class Codes: B01D 67/0067 by carbonisation or pyrolysis
• CPC Class Codes: B01D 67/0095 Drying
• CPC Class Codes: B01D 69/10 Supported membranes; Membrane supports
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: Y02C 20/20 of methane

Abstract

The use of solutions of organic polymers for production of carbon membranes suitable for gas separation, and a process for producing carbon membranes suitable for gas separation, comprising the steps of a) coating a porous substrate with solutions of organic polymers, b) drying the polyester coating on the porous substrate by removing the solvent, and c) pyrolyzing the polyester coating on the porous substrate to form the carbon membrane suitable for gas separation, it being possible to conduct any of steps a) to c) or the sequence of steps a) to c) more than once.

Claims

1. A process for producing a carbon membrane, the process comprising:

producing a surface mesoporous ceramic oxide layer atop a substrate carrier layer by a sol-gel technique, thereby obtaining a porous substrate,

coating the porous substrate with a solution of an organic polymer which can be converted to a carbon membrane by pyrolysis to form a polymer coating,

drying the polymer coating on the porous substrate by removing solvent to form a dry polymer coating, and

pyrolyzing the dry polymer coating on the porous substrate, thereby forming the carbon membrane at a temperature higher than a baking temperature of the porous substrate,

wherein any one of the coating, drying or pyrolyzing or a sequence of the coating, drying and pyrolyzing is optionally conducted more than once, and

the surface mesoporous ceramic oxide layer has a baking temperature below a pyrolysis temperature of the organic polymer.

2. The process according to claim 1, wherein the surface mesoporous ceramic oxide layer has a mean pore diameter in the range of from 2 to 10 nm.

3. The process according to claim 1, wherein the substrate carrier layer is selected from the group consisting of a porous metal, a porous ceramic, a porous glass, and a porous composite thereof.

4. The process according to claim 1, wherein the surface mesoporous ceramic oxide layer is formed from TiO₂, ZrO₂, Al₂O₃, SiO₂, or a mixture thereof.

5. The process according to claim 4, wherein the surface mesoporous ceramic oxide layer is formed from γ

-Al₂O₃.

6. The process according to claim 1, wherein the surface mesoporous ceramic oxide layer in an unbaked form is coated with the solution of the organic polymer.

7. The process according to claim 1, wherein the pyrolyzing is performed at a temperature in the range of from 500 to 900°

C.

8. The process according to claim 1, wherein the organic polymer is at least one selected from cellulose, a polymeric phenolic resin, a melamine resin, a urea resin, a furan resin, a polyimide resin, an epoxy resin, polyfurfuryl alcohol, polyvinyl chloride, polyacrylonitrile, polyethylene, and an ethylenically unsaturated polyester.

9. The process according to claim 8, wherein the ethylenically unsaturated polyester has repeat units of aliphatic diols, aromatic dicarboxylic acids, and ethylenically unsaturated dicarboxylic acids.

10. The process according to claim 9, wherein the aliphatic diols are C_2-12-alkanediols and the ethylenically unsaturated dicarboxylic acids are maleic acids.

11. The process according to claim 8, wherein the solution of ethylenically unsaturated polyester further comprises a crosslinking ethylenically unsaturated monomer and a free-radical former as a crosslinking initiator.

12. The process according to claim 11, wherein the crosslinking ethylenically unsaturated monomer is styrene or α

-methylstyrene.

13. The process according to claim 7, wherein the pyrolyzing is performed at a temperature up to 500°

C. under nitrogen and above 500°

C. under argon.