Composition and system for gas storage

Patent metadata

Field	Value
Publication number	US-10960340-B2
Application number	US-201615573756-A
Country	US
Kind code	B2
Filing date	Jul 8, 2016
Priority date	Jul 8, 2015
Publication date	Mar 30, 2021
Grant date	Mar 30, 2021

Abstract

A composition for gas storage including a mixture of particles of amorphous macroporous organic polymer (MOP) and particles of a metallic organic framework (MOF).

First claim

The invention claimed is:

1. A composition for gas storage comprising a mixture of particles of amorphous microporous organic polymer (MOP) and particles of a metallic organic framework (MOF), wherein the amorphous MOP is a hypercrosslinked polymer comprising optionally substituted aryl groups covalently linked by methylene bridging groups (CH 2 ) to form —(Ar—CH 2 —Ar—CH 2 ) n — wherein n is the number of repeating units.

2. A composition according to claim 1 wherein the particles of amorphous MOP has a BET surface area of at least 600 m 2 /g.

3. A composition according to claim 1 wherein the weight ratio of MOP to MOF in the mixture is in the range of from 1:20 to 20:1.

4. A composition for gas storage according to claim 1 , wherein the particles of MOP and particles of MOF have an average particle size of no more than 0.5 mm.

5. A composition for gas storage according to claim 1 , wherein the composition is in the form of a particulate composite of the particles of amorphous microporous organic polymer (MOP) and particles of a metallic organic framework (MOF) wherein the composite comprises the mixture fused under pressure.

6. A composition for gas storage according to claim 5 , wherein the composite is in the form of shaped articles of the fused mixture having a minimum dimension of at least 1 mm.

7. A composition for gas storage according to claim 1 , wherein the particles of amorphous MOP are disposed in interstitial spaces between MOF particles and are swellable in the presence of the gas to be stored.

8. A composition for gas storage according to claim 1 , wherein the amorphous MOP comprises one or more materials selected from the group consisting of polymers of intrinsic microporosity (PIMS), porous aromatic frameworks (PAFs) and hypercrosslinked polymers.

9. A composition for gas storage according to claim 1 , wherein the methylene bridging groups form covalent links between two adjacent aryl groups to form a six membered carbocyclic ring that is fused with the aryl rings.

10. A composition for gas storage according to claim 1 , wherein the hypercrosslinked polymer is prepared by polymerisation of a substituted aryl monomer comprising at least two chloromethylene groups.

11. A composition for gas storage according to claim 1 , wherein the microporous organic polymer is prepared by polymerisation of an optionally substituted aryl monomer with an external crosslinker preferably selected from monochlorodimethyl ether or dimethyl formal or mixtures thereof, preferably by Friedel Crafts catalysed polymerisation.

12. A composition for gas storage according to claim 1 , wherein the hypercrosslinked polymer is formed by post polymerisation crosslinking of polymers containing aryl monomers preferably selected from optionally substituted vinylbenzyl chloride, vinylbenzyl chloride-co-divinylbenzene copolymers, vinylbenzylchloride copolymers having at least two reactive groups to provide a rigid covalent link between two aryl groups.

13. A composition for gas storage according to claim 1 , wherein the hypercrosslinked polymer is formed by post polymerisation crosslinking using an external cross-linker of polymers containing aryl monomers.

14. A composition for gas storage according to claim 1 , wherein the optionally substituted aryl groups comprise an aryl selected from the group consisting of carbocyclic aryl selected from the group consisting of benzene, biphenyl, naphthylene, tetrahydronaphthylene, idene, azulene, anthracene and heterocyclic aryl selected from the group consisting of furanyl, thiophenyl, 2H-pyrrolyl, pyrrolinyl, oxazolinyl, thiazolinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, isoxazolidinyl, isothiazolinyl, oxadiazolinyl, triazolinyl, thiadiazolinyl, tetrazolinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazenyl, indolyl, isoindolinyl, benzimidazolyl, benzoxazolyl, quinolinyl and isoquinolinyl and optional substituents are selected from the group consisting of C 1 to C 4 alkyl, C 2 to C 4 alkenyl, halo-C 1 to C 4 alkyl, amino, C 1 to C 4 alkylamino, di-(C 1 to C 4 alkyl)amino and sulfonate.

15. A composition for gas storage according to claim 1 , wherein the hypercrosslinked polymer comprises a repeating unit of at least one of formula I or formula II:

wherein n represent the number of repeating units.

16. A composition for gas storage according to claim 1 , wherein the MOF comprises a metal ion or cluster comprising one or more metals selected from elements of groups Ia, IIa, IIIa, Iva to VIIIa and Ib to VIb of the periodic table.

17. A composition for gas storage according to claim 16 , wherein the MOF comprises one or more organic linkers selected from the group consisting of substituted or unsubstituted mono- or poly-nuclear aromatic di-, tri- and tetra-carboxylic acids, esters or amines; and substituted or unsubstituted heteroaromatic di-, tri- and tetra-carboxylic acids, esters or amines which may be mononuclear or polynuclear.

18. A composition for gas storage according to claim 17 , wherein the organic linkers are selected from the group consisting of: benzene tricarboxylate (BTC), ADC (acetylene dicarboxylate), NDC (naphthalene dicarboxylate), BDC (benzene dicarboxylate), ATC (adamantine tetracarboxylate), BTB (benzene tribenzoate), MTB (methane tetrabenzoate) and ATB (adamantine tribenzoate).

19. A composition for gas storage according to claim 1 , wherein the particles of MOF comprises at least one selected from the group consisting of UIO-66, UIO-67, HKUST-1, PCN-14, Al-Fumarate and MOF-210.

20. A composition for gas storage according to claim 1 , wherein the composition is a composite in the form of one or more shaped bodies having a crush strength in the range of from 2 kg to 50 kg.

21. A process for preparation of the composition for gas storage according to claim 1 , the process comprising providing particles of amorphous MOP and particles of MOF, wherein the amorphous MOP is a hypercrosslinked polymer comprising optionally substituted aryl groups covalently linked by methylene bridging groups (CH 2 ) to form (Ar—CH 2 —Ar—CH 2 ) n — wherein n is the number of repeating units, mixing the particles to form a uniform mixture thereof and compressing the mixture to fuse and shape the mixture of particles and form a composite.

22. A process according to claim 21 comprising pressing or extruding the uniform mixture of particles.

23. A process according to claim 21 , wherein the mixture is subject to a temperature in the range of 10° C. to 300° C. and pressure in the range of 1 to 50 tonne.

24. A system for gas storage comprising a container having an entrance for the gas to be stored and optionally a separate exit for the gas to allow the gas to enter and exit the container and a composition for gas storage according to claim 1 , within the container.

25. A system for gas storage according to claim 24 comprising a gas contained within the container.

26. A system for gas storage according to claim 24 , wherein the gas is selected from the group consisting of hydrogen, natural gas, methane, saturated and unsaturated hydrocarbons including: propane, butane, isobutane as well as: phosphine, helium, oxygen, argon, hydrogen sulphide, biogas, arsine, boron trifluoride, carbon monoxide, diborane, trimethylboron, carbon dioxide, dichlorosilane,

Assignees

• Commw Scient Ind Res Org

Inventors

• Wood Colin David
• Mulet Xavier
• Hill Matthew Roland

Classifications

• C08G61/02

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• B01D2253/25

  Coated, impregnated or composite adsorbents · CPC title

• F17C2221/014

  Nitrogen · CPC title

• F17C11/00

  Use of gas-solvents or gas-sorbents in vessels {(absorbing compositions for acetylene C10L3/04; absorbing compositions for hydrogen C01B3/0005)} · CPC title

• F17C11/007

  for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG] · CPC title