Separation membranes formed from perforated graphene and methods for use thereof

• US 9,610,546 B2
• Filed: 09/16/2015
• Issued: 04/04/2017
• Est. Priority Date: 03/12/2014
• Status: Expired due to Fees

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Inventors: Moloney, Padraig, Sinton, Steven W., Bedworth, Peter V., Swett, Jacob L.
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US14/856,198
• Publication Number:
  US 20160074815A1
• Time in Patent Office: 566 Days
• CPC Class Codes: B01D 2053/221 Devices
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2325/20 Specific permeability or cut-off range
• CPC Class Codes: B01D 2325/22 Thermal or heat-resistance properties
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0062 by micromachining techniques, e.g. using masking and etching steps, photolithography
• CPC Class Codes: B01D 67/00791 Different components in separate layers
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/1214 Chemically bonded layers, e.g. cross-linking
• CPC Class Codes: B01D 71/0211 Graphene or derivates thereof
• CPC Class Codes: B01D 71/0281 Zeolites
• CPC Class Codes: C10L 2290/548 Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel
• CPC Class Codes: C10L 3/101 Removal of contaminants
• CPC Class Codes: C10L 3/103 Sulfur containing contaminants
• CPC Class Codes: C10L 3/104 Carbon dioxide
• CPC Class Codes: C10L 3/106 of water
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

Perforated graphene sheets can be used in forming separation membranes. Separation membranes of the present disclosure, which can be used in gas separation processes in some embodiments, can include one or more layers of perforated graphene and one or more layers of another membrane material. Methods for separating a gas mixture can include contacting a gas mixture with the separation membranes, and transiting one or more of the gases through the perforated graphene so as to affect separation.

Claims

1. A composite permeable membrane for separation of a first gas from a second gas;

said composite permeable membrane comprising;

at least one layer of a perforated permeable two-dimensional material; and

at least one membrane of a material other than a two-dimensional material, said membrane being characterized by a permeability for said first gas greater than or equal to 1 Barrer,

wherein said composite permeable membrane is constructed of said at least one layer of the perforated permeable two-dimensional material and said at least one membrane and arranged to provide preferential transport of said first gas relative to said second gas through said at least one membrane and said at least one layer of said perforated permeable two-dimensional material,

wherein said at least one membrane and said at least one layer of said perforated permeable two-dimensional material are provided in a stacked multilayer geometry, and

wherein said each of said at least one layer of said perforated permeable two-dimensional material provided in said stacked multilayer geometry is independently positioned between first and second adjacent membranes.

2. The composite membrane of claim 1, wherein a net gas separation selectivity for said first gas relative to said second gas is greater than or equal to 100.

3. The composite permeable membrane of claim 1, wherein each of said membranes independently provides separation of said first gas and second gas.

4. The composite permeable membrane of claim 1, wherein at least one of said membranes is an inorganic molecular sieve membrane.

5. The composite permeable membrane of claim 1, wherein each of said membranes is capable of exposure to at least one of (a) a pressure of 500 psi without undergoing mechanical failure and (b) temperatures up to 300 K without undergoing chemical or physical degradation.

6. The composite permeable membrane of claim 1, wherein each of said membranes independently has a thickness selected over the range of 0.1 to 50 microns.

7. The composite permeable membrane of claim 1, wherein each of said at least one layer of perforated permeable two-dimensional material is independently characterized by a thickness selected from the range of 0.3 to 5 nm.

8. The composite permeable membrane of claim 1, wherein each of said at least one layer of perforated permeable two-dimensional material is independently characterized by a plurality of holes independently having cross sectional dimensions less than or equal to 10 angstroms.

9. The composite permeable membrane of claim 1, wherein each of said at least one layer of perforated permeable two-dimensional material independently comprises perforated graphene, a perforated graphene-based material, a perforated transition metal dichalcogenide, perforated molybdenum disulfide, perforated α

-boron nitride, silicone, perforated germanene, or a combination thereof.

10. The composite permeable membrane of claim 1, wherein each of said layers of perforated permeable two-dimensional material is independently comprises a perforated permeable graphene-based material.

11. The composite permeable membrane of claim 10, wherein said perforated permeable graphene-based material comprises perforated single-layer graphene, perforated multi-layer graphene or perforated multiple layers of single layer graphene.

12. The composite permeable membrane of claim 1, wherein the first membrane is in physical contact with a first layer of said perforated permeable two-dimensional material.

13. The composite permeable membrane of claim 12, wherein said first layer of said perforated permeable two-dimensional material is provided between, and in physical contact with, said first and second membranes.

19. The composite permeable membrane of claim 1, wherein at least one of a plurality of pores or a surface of the at least one layer of the perforated permeable two-dimensional material is functionalized.

20. The composite permeable membrane of claim 19, wherein the at least one layer of the perforated permeable two-dimensional material is functionalized with moieties of at least one of oxygen, nitrogen, phosphorus, sulfur, fluorine, chlorine, bromide, or iodine.

14. A method for separating a first gas from a second gas;

said method comprising the steps of;

providing a composite permeable membrane comprising;

at least one layer of a perforated permeable two-dimensional material;

at least one membrane of a material other than a two-dimensional material, said membrane being characterized by a permeability for said first gas greater than or equal to 1 Barrer,

wherein said at least one membrane and said at least one layer of said perforated permeable two-dimensional material are provided in a stacked multilayer geometry, and

wherein said each of said at least one layer of said perforated permeable two-dimensional material provided in said stacked multilayer geometry is independently positioned between first and second adjacent membranes;

contacting an external surface of said composite permeable membrane with said first gas and said second gas; and

applying a driving force for transport of the first gas across the composite permeable membrane wherein said composite membrane provides preferential transport of said first gas relative to said second gas through said at least one membrane and said at least one layer of perforated permeable two-dimensional material, thereby separating said first gas from said second gas.

15. The method of claim 14, wherein methane is said second gas and said first gas is selected from the group consisting of CO₂, H₂O, H₂S or any combination of these and the first gas and the second gas are provided in a natural gas.

16. The method of claim 14, providing a method of N₂ purification or CO₂ purification.

17. The method of claim 14, providing a method of revitalizing air.

18. The method of claim 14 wherein at least one of said membranes is an inorganic molecular sieve membrane.