Carbon molecular sieves and methods for making the same

• US 6,562,110 B2
• Filed: 04/12/2001
• Issued: 05/13/2003
• Est. Priority Date: 09/20/2000
• Status: Expired due to Term

• Current Assignee: Chevron USA Incorporated (Chevron Corp.), University of Texas System
• Original Assignee: Chevron USA Incorporated (Chevron Corp.), University of Texas System
• Inventors: Mahajan, Rajiv, Miller, Stephen J., Koros, William J., Vu, De Q.
• Primary Examiner(s): Spitzer, Robert H.
• Application Number:
  US09/834,808
• Publication Number:
  US 20020053284A1
• Time in Patent Office: 761 Days
• Field of Search: 95/51, 95/54, 95/96, 959/03, 961/08, 502/174, 502/180, 502/416, 502/418, 502/428, 502/432, 518/722
• US Class Current: 96/4
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0067 by carbonisation or pyrolysis
• CPC Class Codes: B01D 67/0083 Thermal after-treatment
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/1411 containing dispersed material in a continuous matrix
• CPC Class Codes: B01D 71/0212 Carbon nanotubes
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/28026 Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: Y10S 977/778 within specified host or matrix material, e.g. nanocomposite films
• CPC Class Codes: Y10S 977/783 Organic host/matrix, e.g. lipid
• CPC Class Codes: Y10S 977/786 Fluidic host/matrix containing nanomaterials
• CPC Class Codes: Y10S 977/788 Of specified organic or carbon-based composition
• CPC Class Codes: Y10S 977/882 Assembling of separate components, e.g. by attaching

Abstract

Mixed matrix membranes capable of separating carbon dioxide from mixtures including carbon dioxide and methane, and processes for purifying methane using the membranes, are disclosed. The membranes are preferably polymer membranes, that include discrete carbon-based molecular sieve particles with sizes of between about 0.5 microns to about 5.0 microns. The particles are formed by pyrolyzing a precursor polymer in the form of a powder or film. The pyrolyzed polymer is then ideally milled to desired small size particles. The preferred ratio of particles to polymer is about 0.25 to about 1.0 by volume. A preferred method for preparing the mixed matrix membrane is by dispersing the particles in a solvent, adding a small quantity of the desired polymer or “sizing agent” to “size” or “prime” the particles, adding a polymer, casting a film of the polymer solution, and evaporating the solvent to form a mixed matrix membrane film. The mixed matrix membrane film permits passage of carbon dioxide and methane, but at different permeation rates, such that the ratio of the relative permeation rates of carbon dioxide to methane is larger through the mixed matrix membrane film than through the original polymer. The mixed matrix membrane is preferably in the form of a dense film or a hollow fiber. A mixture containing carbon dioxide and methane can be enriched in methane by selective passage of carbon dioxide over methane in a gas-phase process through the membrane.

Claims

1. A carbon molecular sieve particle comprising a pyrolyzed carbon-based polymer body having numerous ultramicropores therethrough which may act as sieves to substantially inhibit the passage of gas molecules larger than 10 Angstroms in size and wherein the pyrolyzed body is less than 2 microns in size.

2. The sieve particle of claim 1 wherein the ultramicropores substantially inhibit the passage of gas molecules larger than 5 Angstroms in size.

3. The sieve particle of claim 1 wherein the pyrolyzed body is less than 1 micron in size.

4. The sieve particle of claim 1 wherein the pyrolyzed body is between about 0.1 and 0.9 micron in size.

5. The sieve particle of claim 1 wherein the pyrolyzed body is made from a precursor selected from the group consisting of polyetherimides, polyimides, 6FDA/BPDA-DAM, 6FDA-6FpDA, and 6FDA-IPDA.

6. The sieve particle of claim 1 wherein the pyrolyzed body is made from a rigid, glassy polymer.

7. The sieve particle of claim 1 wherein the pyrolyzed body is made from a precursor selected from the group consisting of substituted and unsubstituted polymers and may be selected from polysulfones;

poly(styrenes), including styrene-containing copolymers comprising acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers;

polycarbonates;

cellulosic polymers comprising cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose;

polyamides and polyimides, including aryl polyamides and aryl polyimides;

polyethers;

polyetherimides;

polyetherketones;

poly(arylene oxides) comprising poly(phenylene oxide) and poly(xylene oxide);

poly(esteramide-diisocyanate);

polyurethanes;

polyesters (including polyarylates) comprising poly(ethylene terephthalate), poly(alkyl methacrylates), poly(acrylates), poly(phenylene terephthalate);

polypyrrolones;

polysulfides;

polymers from monomers having alpha-olefinic unsaturation other than mentioned above comprising poly (ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls comprising poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl alcohol), poly(vinyl esters) comprising poly(vinyl acetate) and poly(vinyl propionate), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl ethers), poly(vinyl ketones), poly(vinyl aldehydes) comprising poly(vinyl formal) and poly(vinyl butyral), poly(vinyl amides), poly(vinyl amines), poly(vinyl urethanes), poly(vinyl ureas), poly(vinyl phosphates), and poly(vinyl sulfates);

polyallyls;

poly(benzobenzimidazole);

polyhydrazides;

polyoxadiazoles;

polytriazoles;

poly (benzimidazole);

polycarbodiimides;

polyphosphazines; and

interpolymers, including block interpolymers containing repeating units from the above comprising terpolymers of acrylonitrile-vinyl bromide-sodium salt of para-sulfophenylmethallyl ethers; and

grafts and blends containing any of the foregoing, wherein typical substituents providing substituted polymers include halogens comprising fluorine, chlorine and bromine;

hydroxyl groups;

lower alkyl groups;

lower alkoxy groups;

monocyclic aryl; and

lower acyl groups.

8. The sieve particle of claim 1 wherein the sieve particle is made from a pyrolyzed polyimide.

9. The sieve particle of claim 1 wherein the sieve particle includes a polymer coating.

10. The sieve particle of claim 1 wherein pyrolyzed body is a particle fragment made by fracturing a pyrolyzed polymer;

and the pyrolyzed body having micropores which extend through the body as the result of the fracturing of the pyrolyzed polymer to open otherwise closed ended micropores found in the precursor larger, unfractured pyrolyzed polymer powder.

11. The sieve particle of claim 10 wherein the fracturing of the pyrolyzed polymer is done in a milling process.

12. The sieve particle of claim 1 wherein the pyrolyzed body is made by heating a carbon based precursor polymer above at least 500°

C. for at least two hours.

13. The particle of claim 1 wherein when a collection of such sieve particles are dispersed in a continuous phase polymer and used to prepare a mixed matrix membrane film at about 20 wt. % loading, the membrane shows a pure gas selectivity enhancement of 10% or more in the permeability of CO₂ versus CH₄, compared to a membrane of the same polymer without the sieve particles added.

14. A method for preparing carbon molecular sieves comprising subjecting a polymer powder to pyrolysis conditions to form a carbon molecular sieve, wherein the polymer powder results in an amorphous carbonized structure when pyrolyzed;

and when dispersed in a polymer and used to prepare a mixed matrix membrane film at about 20 wt. % loading, the membrane shows a pure gas selectivity enhancement of 10% or more in the permeability of CO₂ versus CH₄, compared to a membrane of the same polymer without sieve added.

15. A method of preparing carbon molecular sieve particles comprising pyrolyzing a carbon based polymer to create ultramicropores within the pyrolyzed polymer;

and fracturing the pyrolyzed powder until the size of the particles is less than 2 microns in diameter thereby opening up close ended pores formed in the pyrolyzed polymer.

16. The method of claim 15 further comprising separating particles to collect particles of less than 0.9 microns in size.

17. The method of claim 15 wherein the particle is made from a precursor selected from the group consisting of substituted and unsubstituted polymers and may be selected from polysulfones;

poly(styrenes), including styrene-containing copolymers comprising acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers;

polycarbonates;

cellulosic polymers comprising cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose;

polyamides and polyimides, including aryl polyamides and aryl polyimides;

polyethers;

polyetherimides;

polyetherketones;

poly(arylene oxides) comprising poly(phenylene oxide) and poly(xylene oxide);

poly(esteramide-diisocyanate);

polyurethanes;

polyesters (including polyarylates) comprising poly(ethylene terephthalate), poly(alkyl methacrylates), poly(acrylates), and poly(phenylene terephthalate);

polypyrrolones;

polysulfides;

polymers from monomers having alpha-olefinic unsaturation other than mentioned above comprising poly (ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls comprising poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl alcohol), poly(vinyl esters) comprising poly(vinyl acetate) and poly(vinyl propionate), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl ethers), poly(vinyl ketones), poly(vinyl aldehydes) comprising poly(vinyl formal) and poly(vinyl butyral), poly(vinyl amides), poly(vinyl amines), poly(vinyl urethanes), poly(vinyl ureas), poly(vinyl phosphates), and poly(vinyl sulfates);

polyallyls;

poly(benzobenzimidazole);

polyhydrazides;

polyoxadiazoles;

polytriazoles;

poly (benzimidazole);

polycarbodiimides;

polyphosphazines; and

interpolymers, including block interpolymers containing repeating units from the above comprising terpolymers of acrylonitrile-vinyl bromide-sodium salt of para-sulfophenylmethallyl ethers; and

grafts and blends containing any of the foregoing, wherein typical substituents providing substituted polymers include halogens comprising fluorine, chlorine and bromine;

hydrol groups;

lower alkyl groups;

lower alkoxy groups; and

monocyclic aryl; and

lower acyl groups.

18. The method of claim 15 wherein the sieve particles are coated with a carbon based polymer to enhance their ability to be incorporated into a continuous phase polymer.

19. The method of claim 15 wherein the particle is made from a precursor selected from the group consisting of polyetherimides, polyimides, 6FDA/BPDA-DAM, 6FDA-6FpDA, and 6FDA-IPDA.