Gas separations using mixed matrix membranes

• US 6,503,295 B1
• Filed: 09/20/2000
• Issued: 01/07/2003
• 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: Koros, William J., Vu, De Q., Mahajan, Rajiv, Miller, Stephen J.
• Primary Examiner(s): Spitzer, Robert H.
• Application Number:
  US09/666,392
• Time in Patent Office: 839 Days
• Field of Search: 95/45--54, 96/4, 96/8, 96/10, 96/11, 555/24, 55D/IG.5
• US Class Current: 95/51
• 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 polymer membranes with a selective layer thickness of between about 1000 Angstroms to about 0.005 inch, that include discrete carbon-based molecular sieve particles with sizes of between about 0.5 microns to about 5.0 microns. The preferred ratio of particles to polymer is about 20% to about 50% 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 polymer is preferably a rigid, glassy polymer, more preferably, with a glass transition temperature above about 150° C. 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 process for separating two gases having different molecular sizes in the range of about 2.5 Angstroms to about 5.0 Angstroms in a feedstream including these two gas components, the process comprising:

(a) providing a polymer membrane having feed and permeate sides that incorporates carbon-based molecular sieve particles and that is selectively permeable to a first gas component over a second gas component, and

(b) directing a feedstream including the first and second gas components to the feed side of the membrane and withdrawing a retentate stream depleted in the first gas component and withdrawing a permeate stream enriched in the first gas component from the permeate side of the membrane;

wherein the selectivity of the first gas component through the particles is greater than the selectivity of the first gas component through the polymer.

2. The process of claim 1, wherein the first gas is carbon dioxide and the second gas is methane.

3. The process of claim 2, wherein the ratio of carbon dioxide/methane in the feedstream is between about 2% and about 80%.

4. The process of claim 1, wherein the membrane is in the form of a film or a hollow fiber.

5. The process of claim 1, wherein the polymer is a rigid, glassy polymer having a glass transition temperature (Tg) greater than 150°

C.

6. The process of claim 1, wherein the polymer is 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, 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 including terpolymers of acrylonitrile-vinyl bromide-sodium salt of parasulfophenylmethallyl 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.

7. The process of claim 1, wherein the carbon-based molecular sieve is formed by pyrolysis of a polymer selected from the group consisting of those listed in claim 5.

8. The process of claim 1, wherein the polymer is selected from the group having a permeation rate for one gas component through the polymer that is at least 2 times faster than the permeation rate for the other gas component through the polymer.

9. The process of claim 1, wherein the volume ratio of particles to polymer is between about 10% and about 50%.

10. The process of claim 1, wherein the feedstream comprises the product stream from a Fischer-Tropsch reaction.

11. The process of claim 1, wherein the membrane is in the form of a film.

12. The process of claim 1, wherein the membrane is in the form of a hollow fiber.

13. The process of claim 1, wherein at least one of the gases to be separated is selected from the group consisting of carbon dioxide, helium, hydrogen, hydrogen sulfide, oxygen and nitrogen.

14. The process of claim 1, wherein the separation is performed down-hole.

15. The method of claim 1, wherein the membrane is subjected to an annealing treatment by heating it above the glass transition temperature of the polymer.

16. The method of claim 15, wherein the annealing is carried out at a temperature between 10 and 30°

C. above the glass transition temperature.

17. A mixed matrix membrane comprising:

(a) a rigid, glassy polymer and

(b) discrete carbon-based particles dispersed in the polymer;

wherein the membrane is in the form of a film or a hollow fiber,

the thickness of the selective layer of the membrane is between about 1000 Angstroms and about 0.005 in., and

the volume ratio of particles to polymer is between about 10% and about 50%.

18. A method of “

priming”

carbon molecular sieve particles with a polymer, comprising;

(a) dispersing carbon molecular sieve particles in a suitable solvent,

(b) adding a small amount of a polymer to the dispersion, where the polymer is soluble in the solvent, and

(c) adding a non-solvent for the polymer to the dispersion to initiate precipitation of the polymer onto the carbon particles.

19. The method of claim 18, further comprising subjecting the dispersion to ultrasound before step (b).

20. The method of claim 18, further comprising isolating the “

primed”

carbon particles via filtration.

21. The method of claim 20, further comprising drying the “

primed”

carbon particles.