Manufacture of porous carbon membranes

• US 4,919,860 A
• Filed: 07/13/1988
• Issued: 04/24/1990
• Est. Priority Date: 06/25/1986
• Status: Expired due to Fees

• Current Assignee: Akzo Nobel N.V. (Nouryon BV)
• Original Assignee: Akzo Nobel N.V. (Nouryon BV)
• Inventors: Maier, Franz, Schindler, Erich
• Primary Examiner(s): Lorin, Hubert C.
• Application Number:
  US07/218,280
• Time in Patent Office: 650 Days
• Field of Search: 210/500.21, 210/500.23, 210/500.42, 210/500.43, 210/503, 210/505, 210/508, 264/103, 264/29.1, 264/29.2, 264/41, 264/233, 264/85, 264/571, 264/101, 264/102, 264/83, 264/29.6, 264/29.7, 264/129, 264/288.8, 264/289.3, 264/289.6, 264/340, 423/447.2, 423/447.4, 427/112, 427/175, 427/176, 427/226, 427/227
• US Class Current: 264/29.1
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 67/0067 by carbonisation or pyrolysis
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/085 Details relating to the spinneret
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: B01J 35/59 Membranes
• CPC Class Codes: C04B 2111/00801 Membranes; Diaphragms
• CPC Class Codes: C04B 35/52 based on carbon, e.g. graphite
• CPC Class Codes: C04B 35/524 obtained from polymer precursors, e.g. glass-like carbon material
• CPC Class Codes: C04B 38/0022 obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
• CPC Class Codes: D01F 9/22 from polyacrylonitriles

Abstract

The invention relates to a process for making porous carbon membranes and membranes which can made by this process. As starting material, a porous membrane from an acrylonitril-polymer is used. The starting material is pretreated with a hydrazine solution, followed by preoxidation and carbonization. The process enables carbon membranes to be made with selectively adjusted pore sizes and tight pore size distribution. The pore sizes can lie in the ultrafiltration or microfiltration range. The membranes are suitable for separation processes, in which chemically aggressive media are used and for high-temperature processes. They can be used wherever electrical conductivity of the membranes is required.

Claims

1. A process for making porous carbon membranes having a porosity of from 10 to 90% and having maximum pore diameter of from 0.005 to 3 microns in the form of capillary, tubular, or flat membranes and comprising more than 75 weight percent of carbon, comprising:

pretreating a porous membrane from an acrylonitrile polymer in an aqueous hydrazine solution containing at least 40 weight percent of hydrazine,

washing and drying said membrane,

heat treating said membrane in a temperature range of 180°

to 350°

C., and

carbonizing said membrane in a temperature range of 600°

to 3000°

C., whereby clogging of the pores in said membrane is prevented.

2. The process as set forth in claim 1, wherein said aqueous solution contains 50 to 65 weight percent of hydrazine.

3. The process as set forth in claim 1, wherein the pretreatment lasts 15 to 60 minutes in a temperature range of 60°

to 90°

C.

4. The process as set forth in claim 1, further comprising evacuating the pores of the membrane by reduction of pressure and refilling said pores with nitrogen gas at normal pressure prior to the pretreatment.

5. The process as set forth in claim 1, wherein said membrane from an acrylic polymer is unstretched or only partly stretched.

6. The process as set forth in claim 1, wherein at least one of the heat treatment and the carbonization is carried out with complete or extensive shrinkage prevention.

7. The process as set forth in claim 1, wherein the carbonization is carried out in a nitrogen or noble gas atmosphere.

8. The process as set forth in claim 1, wherein the heat treatment is carried out in an air or oxygen atmosphere.

9. The process as set forth in claim 1, wherein the heat treatment is carried out in a temperature range of 200°

to 250°

C.

10. The process as set forth in claim 1, wherein the carbonization is carried out in a temperature range of 800°

to 1600°

C.

11. The process as set forth in claim 1, wherein the carbon membrane produced has a porosity of 50 to 80% and a maximum pore diameter in the range of 0.01 to 1.5 microns.