# US 10,371,320 B2 · Covalent organic framework nanoporous materials for high pressure gas storage

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- Number: US 10,371,320 B2
- Document ID: US10371320B2
- Status: Granted
- Kind: B2
- Application number: 15/532,047
- Filed: 2015-12-01
- Published: 2017-11-02
- Granted: 2019-08-06
- Earliest claimed: 2014-12-01
- Assignees: Blue Wave Co S.A.
- Applicants: Blue Wave Co S.A.
- Inventors: Piero Sozzani; Angiolina Comotti; Silvia Bracco
- Web page: https://patentgrep.com/patent/US10371320B2

## CPC

- F17C 11/007: {for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]}
- 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)}
- B01J 20/267: {Cross-linked polymers}
- B01J 20/28064: {being in the range 500-1000 m2/g}
- B01J 20/28066: {being more than 1000 m2/g}
- B01J 20/28073: {being in the range 0.5-1.0 ml/g}
- B01J 20/28076: {being more than 1.0 ml/g}
- B01J 20/2808: {being less than 2 nm, i.e. micropores or nanopores}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- C08F 132/06: having two or more carbon-to-carbon double bonds
- C08F 132/08: having condensed rings
- C08G 61/124: {with a five-membered ring containing one nitrogen atom in the ring}
- C08G 77/04: Polysiloxanes
- C10L 3/06: Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04 {(liquefying by pressure and cold treatment F25J)}
- F17C 5/06: for filling with compressed gases
- F17C 11/00: Use of gas-solvents or gas-sorbents in vessels {(absorbing compositions for acetylene C10L3/04; absorbing compositions for hydrogen C01B3/0005)}
- F17C 2221/013: Carbon dioxide
- F17C 2221/033: Methane, e.g. natural gas, CNG, LNG, GNL, GNC, PLNG
- F17C 2270/0102: on or in the water
- 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)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS

## Abstract

A method of storing gas comprises providing a recipient for receiving the gas and providing a porous gas storage material. The gas storage material comprises a cross-linked polymeric framework and a plurality of pores for gas sorption. The cross-linked polymeric framework comprises aromatic ring-containing monomeric units comprising at least two aromatic rings. The aromatic ring-containing monomeric units are linked by covalent cross-linking between aromatic rings to form a stable, rigid nanoporous material for storing the gas at pressures significantly greater than the atmospheric pressure, for example in excess of 100 bar. A possible application is the storage and transportation of compressed natural gas.

## Claims

### Claim 1

A method of storing gas, the method comprising:
providing a recipient for receiving the gas;
providing a porous gas storage material, the gas storage material comprising:
a cross-linked polymeric framework; and
a plurality of pores for gas sorption;
wherein the cross-linked polymeric framework comprises aromatic ring-containing monomeric units comprising at least two aromatic rings selected from the group consisting of:
and wherein the aromatic ring-containing monomeric units are linked by covalent cross-linking between aromatic rings; and
loading the recipient with the gas;
the recipient being designed to sustain a nominal maximum internal pressure P1 greater than atmospheric pressure;
the porous gas storage material being disposed within said recipient; and
loading the recipient with the gas to a pressure P2 equal to or lower than P1.

### Claim 2 (depends on 1)

The method of claim 1, wherein P2 is greater than N bar, wherein N is an integer in the interval 2-180.

### Claim 3 (depends on 1)

The method of claim 1, wherein P1 is greater than M bar, wherein M is an integer equal to 5, or a multiple thereof, in the interval 10-250.

### Claim 4 (depends on 1)

The method of claim 1, wherein the gas comprises methane, it being optionally compressed natural gas (CNG), it being optionally raw CNG.

### Claim 5 (depends on 4)

The method of claim 4, wherein the recipient is a pressure vessel designed to store, or store and transport, the CNG, it being optionally for marine storage, or storage
and transportation, of the CNG onboard a water-going naval craft.

### Claim 6 (depends on 5)

The method of claim 5, wherein the pressure vessel comprises a load-bearing structural portion comprising a composite material.

### Claim 7 (depends on 5)

The method of claim 5, wherein the pressure vessel comprises a load-bearing structural portion comprising a filamentous composite material.