Adsorbent-assisted stabilization of highly reactive gases

• US 10,940,426 B2
• Filed: 09/24/2018
• Issued: 03/09/2021
• Est. Priority Date: 09/25/2017
• Status: Active Grant

• Current Assignee: NuMat Technologies, Inc.
• Original Assignee: NuMat Technologies, Inc.
• Inventors: Tom, Glenn M., Siu, Paul Wai-Man, Arno, Jose, Farha, Omar K., Verploegh, Ross
• Primary Examiner(s): Robinson, Renee
• Application Number:
  US16/139,958
• Publication Number:
  US 20190091620A1
• Time in Patent Office: 897 Days
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/204 Metal organic frameworks (MOF's)
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2257/204 Inorganic halogen compounds
• CPC Class Codes: B01D 2257/40 Nitrogen compounds
• CPC Class Codes: B01D 2257/553 Compounds comprising hydrogen, e.g. silanes
• CPC Class Codes: B01D 2257/93 Toxic compounds not provided for in groups B01D2257/00 - B01D2257/708
• 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 53/0415 Beds in cartridges
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• 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 20/28078 Pore diameter
• CPC Class Codes: F17C 11/00 Use of gas-solvents or gas-sorbents in vessels absorbing compositions for acetylene C10L3/04; absorbing compositions for hydrogen C01B3/0005
• CPC Class Codes: Y02E 60/32 Hydrogen storage

Abstract

A method of adsorbing a highly reactive gas onto an adsorbent material comprising adsorbing the highly reactive gas to the adsorbent material. The adsorbent material comprises at least one Lewis basic functional group, or pores of a size to hold a single molecule of the highly reactive gas, or inert moieties which are provided to the adsorbent material at the same time at the same time as the highly reactive gas, prior to adsorbing the highly reactive gas or after adsorbing the highly reactive gas, or the highly reactive gas reacts with moieties of the adsorbent material resulting in passivation of the adsorbent material. A rate of decomposition of the adsorbed highly reactive gas is lower than a rate of decomposition for the neat gas at equal volumetric loadings and equal temperatures for both the adsorbed highly reactive gas and the neat gas.

Claims

1. A method of adsorbing a highly reactive gas onto a metal-organic framework (MOF) comprising:

reacting an initial dose of the highly reactive gas with the MOF, wherein the initial dose of the highly reactive gas passivates the MOF in a first adsorption cycle so that a rate of decomposition of the adsorbed highly reactive gas during subsequent adsorption cycles is lower than a rate of decomposition of the adsorbed highly reactive gas during the first adsorption cycle; and

adsorbing an additional dose of the highly reactive gas to the MOF subsequent to the initial dose.

2. The method of claim 1, wherein the adsorbed highly reactive gas is arsine (AsH₃), stibine (SbH₃), phosphine (PH₃), borane (BH₃), diborane (B₂H₆), halides, germane, digermane, silane, disilane, hydrazine or nitrogen trifluoride.

3. The method of claim 1, further comprising removing byproducts formed by the reaction of the initial dose of the highly reactive gas with the MOF prior to adsorbing the highly reactive gas to the MOF subsequent to the initial dose.

4. The method of claim 1, further comprising raising at least one of temperature or pressure to accelerate passivation of the MOF.

5. A gas storage and dispensing apparatus for a highly reactive gas comprising:

a container; and

an adsorbent material located in the container, wherein the adsorbent material comprises;

inert moieties which do not chemically react with the highly reactive gas; and

wherein a combination of the adsorbent material and the inert moieties is configured to provide a rate of decomposition of the adsorbed highly reactive gas lower than a rate of decomposition for a neat highly reactive gas that is not adsorbed at equal volumetric loadings and equal temperature for both the adsorbed highly reactive gas and the neat highly reactive gas.

6. The apparatus of claim 5, wherein the adsorbent material comprises a metal-organic framework (MOF).

7. The apparatus of claim 5, wherein the adsorbent material comprises a porous organic polymer (POP).

8. The apparatus of claim 5, wherein the adsorbent material comprises activated carbon.

9. The apparatus of claim 5, wherein the adsorbent material further comprises:

at least one Lewis basic functional group;

or

pores of a size to hold a single molecule of the highly reactive gas.

10. The apparatus of claim 5, wherein the adsorbed highly reactive gas is arsine (AsH₃), stibine (SbH₃), phosphine (PH₃), borane (BH₃), diborane (B₂H₆), halides, germane, digermane, silane, disilane, hydrazine or nitrogen trifluoride.