Functionalization of zeolites

• US 20190329214A1
• Filed: 04/19/2019
• Published: 10/31/2019
• Est. Priority Date: 04/30/2018
• Status: Active Grant

• Current Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Inventors: Falconer, John L., Medlin, James William, Ellis, Lucas Delano, Funke, Hans H., Parker, Surya
• Granted Patent: US 11,918,974 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2253/306 Surface area, e.g. BET-specific surface
• CPC Class Codes: B01D 2256/24 Hydrocarbons
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/7022 Aliphatic hydrocarbons
• CPC Class Codes: B01D 2257/7025 Methane
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01J 20/186 Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/28016 Particle form
• CPC Class Codes: B01J 20/3071 Washing or leaching
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: C01B 39/026 After-treatment
• CPC Class Codes: C07C 11/06 Propene
• CPC Class Codes: C07C 7/13 by molecular-sieve technique
• CPC Class Codes: C07C 9/04 Methane production by treatment of sewage C02F11/04; natural gas, synthetic natural gas C10L3/06
• CPC Class Codes: C07C 9/06 Ethane
• CPC Class Codes: C07C 9/08 Propane
• CPC Class Codes: C07C 9/10 : with four carbon atoms
• CPC Class Codes: Y02C 20/20 : of methane
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2
• CPC Class Codes: Y02P 20/156 : Methane [CH4]
• CPC Class Codes: Y02P 20/50 : Improvements relating to the production of bulk chemicals

Abstract

Functionalized zeolites, including a zeolite substrate and a self-assembled monolayer of a phosphonic acid on a surface of the zeolite substrate, are disclosed, as are methods of making and using the functionalized zeolites. The disclosed methods and compositions have various applications, including in the use of molecular sieves to separate small-molecule gases from mixtures thereof. Gas adsorption selectivities and diffusion rates of the functionalized zeolites may be tuned or selected according to the disclosed methods.

Claims

1. A method for functionalizing a zeolite, comprising:

(a) providing a zeolite;

(b) mixing the zeolite into a solution of a phosphonic acid in a first organic solvent to form a slurry;

(c) stirring and centrifuging the slurry and decanting a liquid fraction thereof to form a modified powder;

(d) washing or rinsing the modified powder with a second organic solvent; and

(e) removing the second organic solvent to obtain the functionalized zeolite.

2. The method of claim 1, wherein step (a) comprises calcining and subsequently cooling a zeolite material.

3. The method of claim 1, wherein the zeolite is selected from the group consisting of zeolite 5A, SAPO-34 zeolite, MFI zeolites, chabazite, Y zeolite, faujasite, ferrierite, mordenite, SSZ-13 zeolite, and ZSM-5 zeolite.

4. The method of claim 1, wherein the organic tail of the phosphonic acid comprises between one and eighteen carbon atoms.

5. The method of claim 1, further comprising, between steps (c) and (d), annealing the modified powder.

6. A functionalized zeolite, comprising:

a zeolite substrate; and

a self-assembled monolayer of a phosphonic acid, disposed on a surface of the zeolite substrate.

7. The functionalized zeolite of claim 6, wherein the zeolite substrate is annealed.

8. The functionalized zeolite of claim 6, wherein the zeolite substrate comprises at least one of a powder and a pellet.

9. The functionalized zeolite of claim 6, wherein the zeolite substrate comprises at least one zeolite selected from the group consisting of zeolite 5A, SAPO-34 zeolite, WI zeolites, chabazite, Y zeolite, faujasite, ferrierite, mordenite, SSZ-13 zeolite, and ZSM-5 zeolite.

10. The functionalized zeolite of claim 6, wherein the organic tail of the phosphonic acid comprises between one and eighteen carbon atoms.

11. The functionalized zeolite of claim 6, wherein the zeolite substrate comprises zeolite 5A and the phosphonic acid is methylphosphonic acid.

12. The functionalized zeolite of claim 6, wherein at least a portion of the monolayer is disposed on or within a pore of the zeolite substrate.

13. The functionalized zeolite of claim 6, wherein at least one of the following is true:

(i) the functionalized zeolite has a propylene/propane ideal adsorption selectivity of at least about 45;

(ii) the functionalized zeolite has an ethane/propane ideal adsorption selectivity of at least about 44; and

(iii) the functionalized zeolite has an ethane/n-butane ideal adsorption selectivity of at least about 13.

14. The functionalized zeolite of claim 6, wherein an organic tail of the phosphonic acid comprises at least one of an alkyl chain having between one and eighteen carbon atoms, a branched alkyl group, an unsaturated hydrocarbon including at least one carbon-carbon double (alkene) or triple (alkyne) bond, a haloalkane, a haloarene, an alcohol, an ether, an aldehyde, a ketone, a carboxylic acid, a carboxylate, an ester, an acyl group, an acyl halide, an acid anhydrides, an amine, an amide, a nitrile, an aromatic group, a nonaromatic cyclic group, an organosulfur, an organophosphorus, and an organometallic

15. A method for separating a first chemical compound from a mixture comprising the first chemical compound and a second chemical compound, the method comprising:

contacting the mixture with a functionalized zeolite to selectively sorb the first chemical compound, the functionalized zeolite comprising a zeolite substrate and a self-assembled monolayer of a phosphonic acid disposed on a surface of the zeolite substrate.

16. The method of claim 15, wherein at least one of the first chemical compound and the second chemical compound is selected from the group consisting of carbon dioxide, methane, ethylene, ethane, ethanol, propylene, propane, propanol, butadiene, 1-butene, 2-butene, isobutene, n-butane, isobutane, water, oxygen, and nitrogen.

17. The method of claim 16, wherein the first chemical compound is propane and the second chemical compound is propylene or vice versa, and wherein the zeolite substrate comprises zeolite 5A and the phosphonic acid is methylphosphonic acid.

18. The method of claim 17, wherein the functionalized zeolite has a propylene/propane ideal adsorption selectivity of at least about 45.

19. The method of claim 15, wherein the zeolite substrate comprises at least one zeolite selected from the group consisting of zeolite 5A, SAPO-34 zeolite, MFI zeolites, chabazite, Y zeolite, faujasite, ferrierite, mordenite, SSZ-13 zeolite, and ZSM-5 zeolite.

20. The method of claim 16, wherein an organic tail of the phosphonic acid comprises at least one of an alkyl chain having between one and eighteen carbon atoms, a branched alkyl group, an unsaturated hydrocarbon including at least one carbon-carbon double (alkene) or triple (alkyne) bond, a haloalkane, a haloarene, an alcohol, an ether, an aldehyde, a ketone, a carboxylic acid, a carboxylate, an ester, an acyl group, an acyl halide, an acid anhydrides, an amine, an amide, a nitrile, an aromatic group, a nonaromatic cyclic group, an organosulfur, an organophosphorus, and an organometallic.