# US 10,870,101 B2 · Metal organic frameworks for gas storage

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- Number: US 10,870,101 B2
- Document ID: US10870101B2
- Status: Granted
- Kind: B2
- Application number: 16/402,597
- Filed: 2019-05-03
- Published: 2019-08-22
- Granted: 2020-12-22
- Earliest claimed: 2014-12-04
- Assignees: King Abdullah University of Science and Technology
- Applicants: King Abdullah University of Science and Technology
- Inventors: Dalal Alezi; Youssef Belmabkhout; Mohamed Eddaoudi
- Web page: https://patentgrep.com/patent/US10870101B2

## CPC

- 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)}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01D 53/0476: {Vacuum pressure swing adsorption}
- B01D 53/047: Pressure swing adsorption
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2257/104: Oxygen
- B01D 2257/7025: Methane
- B01D 2258/05: Biogas
- B01D 2259/4525: for storage and dispensing systems
- F17C 11/007: {for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]}
- Y02C 20/20: of methane
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- F17C: VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES (storing fluids in natural or artificial cavities or chambers in the earth B65G5/00; construction or assembling of bulk storage containers employing civil-engineering techniques E04H7/00; variable-capacity gas-holders F17B; liquefaction or refrigeration machines, plants, or systems F25)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## Abstract

Embodiments of the present disclosure describe methods of removing one or more compounds from a fluid comprising contacting a metal-organic framework (MOF) composition having a square-octahedral topology with a fluid containing one or more of CH4 and O2, sorbing one or more of CH4 and O2 with the MOF composition, and storing one or more of the CH4 and O2 with the MOF composition.

## Claims

### Claim 1

A method of removing one or more compounds from a fluid, comprising:
contacting a metal-organic framework (MOF) composition having a square-octahedral topology with a fluid containing one or more of CH4 and O2, wherein the MOF composition includes an organic ligand and a metal selected from aluminum, gallium, iron, scandium, titanium, chromium, and vanadium;
sorbing one or more of CH4 and O2 with the MOF composition; and
storing one or more of the CH4 and O2 with the MOF composition.

### Claim 2 (depends on 1)

The method of claim 1, wherein the organic ligand is selected from tetradentate organic ligands.

### Claim 3 (depends on 1)

The method of claim 1, wherein the organic ligand is selected from tetracarboxylate ligands.

### Claim 4 (depends on 1)

The method of claim 1, wherein the organic ligand is selected from rectangular planar organic ligands.

### Claim 5 (depends on 1)

The method of claim 1, wherein the organic ligand is selected from: amidetetracarboxylate, 3,3′,5,5′-azobenzenetetracarboxylate, TCPT, TCDPN, TCDPA, 2″,3″,5″,6″-tetrabromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″″-dicarboxylic acid, 2″,3″,5″-tribromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″-dicarboxylic acid, 2″,5″-dibromo-5′,5″-bis(4-carboxyphenyl)-[1, 1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″-dicarboxylic acid, 2″,3″-dibromo-5′,5″′-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″″-dicarboxylic acid, 5′,5″-bis(4-carboxyphenyl)-2″-(trifluoromethyl)-[1,1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″″-dicarboxylic acid, 5′,5″-bis(4-carboxyphenyl)-2″,5″-bis(trifluoromethyl)-[1,1′:3′,1″:4″, 1′″: 3′″, 1″″-quinquephenyl]-4,4″″-dicarboxylic acid, 3,3′,3″,3′″-([1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayl)tetrapropiolic acid, 3,3′,3″,3′″-(ethyne-1,2-diylbis(benzene-5,1,3-triyl))tetrapropiolic acid, 3,3′,3″,3′″-(2′,3′,5′,6′-tetramethyl-[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayl)tetrapropiolic acid, 3,3′,3″,3′″-(ethyne-1,2-diylbis(2,4,6-trimethylbenzene-5,1,3-triyl))tetrapropiolic acid, 4,4′,4″,4″-([1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, 4,4′,4″,4′″-(((1,4-phenylenebis(ethyne-2,1-diyl))bis(benzene-5,1,3-triyl))tetrakis(ethyne-2,1-diyl))tetrabenzoic acid, 5″,5″″″′-(1,4-phenylenebis(ethyne-2,1-diyl))bis(([1,1′:4′, 1″:3″,1′″:4′″, 1″-quinquephenyl]-4,4″-dicarboxylic acid)), 5″,5″″″′-(1,4-phenylenebis([1,1′:4′, 1″:3″,1′″:4′″, 1″-quinquephenyl]-4,4″-dicarboxylic acid)), 0026BIS, 5,5′-(ethane-1,2-diyl)diisophthalic acid, (E)-5,5′-(diazene-1,2-diyl)diisophthalic acid, (E)-5,5′-(ethene-1,2-diyl)diisophthalic acid, 5,5′-(ethyne-1,2-diyl)diisophthalic acid, (Z)-1,2-bis(3,5-dicarboxyphenyl)diazene 1-oxide, LigandC42H26O8, 4,4′,4″,4′″-(1,4-phenylenebis(azanetriyl))tetrabenzoic acid, and combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the MOF composition stores one or more of CH4 and O2 at temperatures ranging from about −80° C. to about 125° C.

### Claim 7 (depends on 1)

The method of claim 1, wherein the MOF composition stores one or more of CH4 and O2 at pressures up to about 85 bar or less.

### Claim 8 (depends on 1)

The method of claim 1, further comprising desorbing one or more of the CH4 and O2.

### Claim 9 (depends on 8)

The method of claim 8, wherein heat is not required to desorb one or more of the CH4 and O2.

### Claim 10 (depends on 1)

The method of claim 1, wherein the fluid comprises one or more of natural gas and biogas.

### Claim 11

A method of removing one or more compounds from a fluid, comprising:
contacting a metal-organic framework (MOF) composition having a square-octahedral topology with a fluid containing one or more of CH4 and O2, wherein the MOF composition includes an organic ligand and a metal selected from aluminum, gallium, iron, scandium, titanium, chromium, and vanadium;
sorbing one or more of CH4 and O2 with the MOF composition;
storing one or more of the CH4 and O2 with the MOF composition; and
desorbing one or more of the CH4 and O2 from the MOF composition.

### Claim 12 (depends on 11)

The method of claim 11, wherein the organic ligand is selected from: amidetetracarboxylate, 3,3′,5,5′-azobenzenetetracarboxylate, TCPT, TCDPN, TCDPA, 2″,3″,5″,6″-tetrabromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″″-dicarboxylic acid, 2″,3″,5″-tribromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″-dicarboxylic acid, 2″,5″-dibromo-5′,5″-bis(4-carboxyphenyl)-[1, 1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″-dicarboxylic acid, 2″,3″-dibromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1′″:3′″, 1″-quinquephenyl]-4,4″-dicarboxylic acid, 5′,5″-bis(4-carboxyphenyl)-2″-(trifluoromethyl)-[1,1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″″-dicarboxylic acid, 5′,5″-bis(4-carboxyphenyl)-2″,5″-bis(trifluoromethyl)-[1,1′:3′,1″:4″,1′″:3′″,1″-quinquephenyl]-4,4″-dicarboxylic acid, 3,3′,3″,3′″-([1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayl)tetrapropiolic acid, 3,3′,3″,3′″-(ethyne-1,2-diylbis(benzene-5,1,3-triyl))tetrapropiolic acid, 3,3′,3″,3′″-(2′,3′,5′,6′-tetramethyl-[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayl)tetrapropiolic acid, 3,3′,3″,3′″-(ethyne-1,2-diylbis(2,4,6-trimethylbenzene-5,1,3-triyl))tetrapropiolic acid, 4,4′,4″,4″-([1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, 4,4′,4″,4′″-(((1,4-phenylenebis(ethyne-2,1-diyl))bis(benzene-5,1,3-triyl))tetrakis(ethyne-2,1-diyl))tetrabenzoic acid, 5″,5″″″′-(1,4-phenylenebis(ethyne-2,1-diyl))bis(([1,1′:4′,1″:3″,1′″:4′″,1″″-quinquephenyl]-4,4″-dicarboxylic acid)), 5″,5″″″′-(1,4-phenylenebis([1,1′:4′,1″:3″,1′″:4′″, 1″″-quinquephenyl]-4,4″-dicarboxylic acid)), 0026BIS, 5,5′-(ethane-1,2-diyl)diisophthalic acid, (E)-5,5′-(diazene-1,2-diyl)diisophthalic acid, (E)-5,5′-(ethene-1,2-diyl)diisophthalic acid, 5,5′-(ethyne-1,2-diyl)diisophthalic acid, (Z)-1,2-bis(3,5-dicarboxyphenyl)diazene 1-oxide, LigandC42H26O8, 4,4′,4″,4′″-(1,4-phenylenebis(azanetriyl))tetrabenzoic acid, and combinations thereof.

### Claim 13 (depends on 11)

The method of claim 11, wherein the MOF composition stores one or more of CH4 and O2 at temperatures ranging from about −80° C. to about 125° C. and/or at pressures up to about 85 bar or less.

### Claim 14

A method of removing one or more compounds from a fluid, comprising:
contacting a metal-organic framework (MOF) composition having a square-octahedral topology with a fluid comprising one or more of natural gas and biogas, wherein the MOF composition includes an organic ligand and a metal selected from aluminum, gallium, iron, scandium, titanium, chromium, and vanadium;
sorbing one or more of CH4 and O2 with the MOF composition; and
storing one or more of the CH4 and O2 with the MOF composition.

### Claim 15 (depends on 14)

The method of claim 14, wherein the organic ligand is selected from: amidetetracarboxylate, 3,3′,5,5′-azobenzenetetracarboxylate, TCPT, TCDPN, TCDPA, 2″,3″,5″,6″-tetrabromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″″-dicarboxylic acid, 2″,3″,5″-tribromo-5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″, 1″-quinquephenyl]-4,4″-dicarboxylic acid, 2″,5″-dibromo-5′,5″-bis(4-carboxyphenyl)-[1, 1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″-dicarboxylic acid, 2″,3″-dibromo-5′,5″′-bis(4-carboxyphenyl)-[1,1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″″-dicarboxylic acid, 5′,5″-bis(4-carboxyphenyl)-2″-(trifluoromethyl)-[1,1′:3′,1″:4″,1″′:3′″,1″-quinquephenyl]-4,4″″-dicarboxylic acid, 5′,5″-bis(4-carboxyphenyl)-2″,5″-bis(trifluoromethyl)-[1,1′:3′,1″:4″,1′″:3′″,1″-quinquephenyl]-4,4″-dicarboxylic acid, 3,3′,3″,3′″-([1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayl)tetrapropiolic acid, 3,3′,3″,3′″-(ethyne-1,2-diylbis(benzene-5,1,3-triyl))tetrapropiolic acid, 3,3′,3″,3′″-(2′,3′,5′,6′-tetramethyl-[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayl)tetrapropiolic acid, 3,3′,3″,3′″-(ethyne-1,2-diylbis(2,4,6-trimethylbenzene-5,1,3-triyl))tetrapropiolic acid, 4,4′,4″,4″-([1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, 4,4′,4″,4′″-(((1,4-phenylenebis(ethyne-2,1-diyl))bis(benzene-5,1,3-triyl))tetrakis(ethyne-2,1-diyl))tetrabenzoic acid, 5″,5″″″′-(1,4-phenylenebis(ethyne-2,1-diyl))bis(([1,1′:4′,1″:3″,1′″:4″, 1″-quinquephenyl]-4,4″-dicarboxylic acid)), 5″,5″″″′-(1,4-phenylenebis([1,1′:4′, 1″:3″,1′″:4′″, 1″″-quinquephenyl]-4,4″″-dicarboxylic acid)), 0026BIS, 5,5′-(ethane-1,2-diyl)diisophthalic acid, (E)-5,5′-(diazene-1,2-diyl)diisophthalic acid, (E)-5,5′-(ethene-1,2-diyl)diisophthalic acid, 5,5′-(ethyne-1,2-diyl)diisophthalic acid, (Z)-1,2-bis(3,5-dicarboxyphenyl)diazene 1-oxide, LigandC42H26O8, 4,4′,4″,4′″-(1,4-phenylenebis(azanetriyl))tetrabenzoic acid, and combinations thereof.

### Claim 16 (depends on 14)

The method of claim 14, wherein the MOF composition stores one or more of CH4 and O2 at temperatures ranging from about −80° C. to about 125° C.

### Claim 17 (depends on 14)

The method of claim 14, wherein the MOF composition stores one or more of CH4 and O2 at pressures up to about 85 bar or less.

### Claim 18 (depends on 14)

The method of claim 14, further comprising desorbing one or more of the CH4 and O2.

### Claim 19 (depends on 18)

The method of claim 18, wherein heat is not required to desorb one or more of the CH4 and O2.