Metal organic framework absorbent platforms for removal of CO2 and H2S from natural gas

• US 10,328,380 B2
• Filed: 04/07/2016
• Issued: 06/25/2019
• Est. Priority Date: 04/07/2015
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Eddaoudi, Mohamed, Cadiau, Amandine, Bhatt, Prashant M., Adil, Karim, Belmabkhout, Youssef
• Primary Examiner(s): Berns, Daniel
• Application Number:
  US15/564,935
• Publication Number:
  US 20180093218A1
• Time in Patent Office: 1,174 Days
• Field of Search: None
• CPC Class Codes: B01D 2253/116 Molecular sieves other than zeolites
• CPC Class Codes: B01D 2253/204 Metal organic frameworks (MOF's)
• 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 2259/40007 Controlling pressure or temperature swing adsorption
• 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: B01D 53/0476 Vacuum pressure swing adsorption
• CPC Class Codes: B01J 20/226 Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28069 Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/3425 of sorbents or filter aids comprising organic materials
• CPC Class Codes: B01J 20/3483 by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• CPC Class Codes: B01J 20/3491 by pressure treatment
• CPC Class Codes: C07F 15/02 Iron compounds
• CPC Class Codes: C07F 15/04 Nickel compounds
• CPC Class Codes: C07F 5/066 compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
• CPC Class Codes: C07F 9/00 Compounds containing elements of Groups 5 or 15 of the Periodic Table
• CPC Class Codes: C10L 2290/542 Adsorption of impurities during preparation or upgrading of a fuel
• CPC Class Codes: C10L 3/103 : Sulfur containing contaminants
• CPC Class Codes: C10L 3/104 : Carbon dioxide
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands which have high selectivity and stability in the present of gases and vapors including H₂S, H₂O, and CO₂. Methods include capturing one or more of H₂S, H₂O, and CO₂ from fluid compositions, such as natural gas.

Claims

1. A method of capturing chemical species from a fluid composition, the method comprising

contacting a first metal organic framework characterized by the formula [M_aM_bF_6-n(O/H₂O)_w(Ligand)_x(solvent)_y]_z with a fluid composition including at least carbon dioxide and hydrogen sulfide, where M_a is Ni²⁺;

M_b is Al³⁺, Fe³⁺, V³⁺ or Nb⁵⁺;

Ligand is pyrazine;

n is 1;

w is 1;

x is 2;

v is 0 to 4;

solvent is a guest molecule; and

z is at least equal to 1; and

capturing carbon dioxide and hydrogen sulfide from the fluid composition.

2. The method of claim 1, wherein the fluid composition further comprises water.

3. The method of claim 1, further comprising desorbing carbon dioxide and hydrogen sulfide.

4. The method of claim 1, further comprising desorbing one or more of carbon dioxide and hydrogen sulfide.

5. The method of claim 4, wherein one or more of capturing and desorbing is effected by multicolumn pressure-temperature swing adsorption.

6. The method of claim 1, wherein carbon dioxide and hydrogen sulfide are captured from the fluid composition simultaneously.

7. The method of claim 1, wherein the metal-organic framework has open metal sites.

8. The method of claim 1, wherein the metal organic framework adsorbent is in the form of a fixed bed, a packed column, or combinations thereof.

9. The method of claim 1, wherein the fluid composition further comprises methane.

10. The method of claim 1, further comprising changing the pressure of the capture environment to alter the affinity of one or more of carbon dioxide and hydrogen sulfide for the metal organic framework adsorbent.

11. The method of claim 1, further comprising changing the temperature of the capture environment to alter the affinity of one or more of carbon dioxide and hydrogen sulfide for the metal organic framework adsorbent.

12. The method of claim 1, further comprising changing the pressure and temperature of the capture environment to alter the affinity of one or more of carbon dioxide and hydrogen sulfide for the metal organic framework adsorbent.

13. The method of claim 1, wherein capturing comprises physical adsorption of the one or more captured chemical species by the metal organic framework.

14. The method of claim 1, wherein capturing comprises chemisorption of the one or more captured chemical species by the metal organic framework.

15. The method of claim 14, wherein chemisorption occurs by one or more captured chemical species chemically interacting with one or more open metal sites of the metal organic framework.

16. The method of claim 1, simultaneously or separately contacting the fluid composition with a second metal organic framework, characterized by the formula [M_cM_dF_6-n(O/H₂O)_w(Ligand)_x(solvent)_y]_z, wherein n is 1;

w is 1;

x is 2;

y is 0 to 4; and

solvent is a guest molecule;

wherein M_c comprises Ni⁺² and M_d comprises Al⁺³, Fe⁺², or Fe⁺³, wherein the second metal organic framework is different from the first metal organic framework.

17. The method of claim 16, wherein the first metal organic framework is characterized by the formula [NiNbF_6-n(O/H₂O)_w(Ligand)_x(solvent)_y]_z;

wherein n is 1;

w is 1;

x is 2;

y is 0 to 4; and

solvent is a guest molecule.