Shaped bodies containing metal-organic frameworks

• US 6,893,564 B2
• Filed: 05/30/2002
• Issued: 05/17/2005
• Est. Priority Date: 05/30/2002
• Status: Expired due to Term

• Current Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Original Assignee: BASF AG (BASF SE), Board of Regents of the University of Michigan (University of Michigan)
• Inventors: Hesse, Michael, Mueller, Ulrich, Eddaoudi, Mohamed, Yaghi, Omar, Lobree, Lisa
• Primary Examiner(s): KIM, SUN U
• Application Number:
  US10/157,182
• Publication Number:
  US 20030222023A1
• Time in Patent Office: 1,083 Days
• Field of Search: 210/502.1, 210/503, 210/510.1, 210/502, 502/150, 502/151, 502/152, 502/153, 502/154, 502/401, 540/465, 554/225, 264/239
• US Class Current: 210/502.1
• CPC Class Codes: B01D 2257/93 Toxic compounds not provided for in groups B01D2257/00 - B01D2257/708
• 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 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28011 Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/28014 characterised by their form
• CPC Class Codes: B01J 20/2803 Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/28045 Honeycomb or cellular structures; Solid foams or sponges
• CPC Class Codes: B01J 20/281 Sorbents specially adapted for preparative, analytical or investigative chromatography
• CPC Class Codes: B01J 20/282 Porous sorbents ion exchange B01J39/00 - B01J41/00
• CPC Class Codes: B01J 20/3007 Moulding, shaping or extruding
• CPC Class Codes: B01J 20/3042 Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: B01J 2220/82 Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
• CPC Class Codes: B01J 31/1691 Coordination polymers, e.g. metal-organic frameworks [MOF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 39/16 Organic material
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C02F 1/28 by sorption using ion-exchange C02F1/42; sorbent compositions B01J
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J

Abstract

The present invention relates to a novel class of shaped bodies containing metal-organic frameworks. Said metal-organic frameworks comprise at least one metal ion and at least one at least bidentate organic compound and contain at least one type of micro- and mesopores or micro- or mesopores. Said shaped bodies comprise at least one metal-organic framework material and may optionally contain further substances, in particular at least one supporting material.

Claims

1. A shaped body comprising a porous metal-organic framework material, prepared by molding a composition comprising a porous metal-organic framework material or contacting at least one substrate with at least one metal-organic framework material, wherein said metal-organic framework material comprises at least one metal ion and at least one at least bidentate organic compound which is coordinately bonded to said metal ion;

wherein the shaped body extends in at least one direction in space by at least 0.02 mm and does not extend in any direction in space by more than 50 mm; and

wherein the shaped body has a resistance to pressure (crush strength) in the range of from 2 N to 100 N.

2. The shaped body according to claim 1, wherein the shaped body is in the form of a pellet having a diameter in the range from 1.5 mm to 5 mm and a height in the range from 1 mm to 5 mm.

3. A process for preparing the shaped body according to claim 1, wherein the shaped body is prepared by at least one step of molding a composition comprising a porous metal-organic framework material.

4. The process according to claim 3, wherein said molding is selected from the group consisting of briquetting by piston presses, briquetting by roller pressing, binderless briquetting, briquetting with binders, pelleting, compounding, melting, extruding, co-extruding, spinning, deposition, foaming, spray drying, coating, granulating and spray granulating.

5. The process according to claim 3, wherein the composition further comprises at least one binder, and the binder is selected from the group consisting of a hydrated alumina or other aluminum containing binders, mixers of silicon and aluminum compounds, silicon compounds, clay minerals, alkoxysilanes, amphiphilic substances and graphite.

6. A process for preparing a shaped body according to claim 1, comprising contacting at least one substrate with at least one metal-organic framework material.

7. The process according to claim 6, wherein said contacting is selected from the group consisting of impregnating said substrate with a fluid comprising the metal-organic framework material, soaking said substrate in a fluid comprising the metal-organic framework material, spraying said substrate the metal-organic framework material, depositing the metal-organic framework material from the liquid phase on the substrate, depositing the metal-organic framework material from the gas phase (vapor deposition) on the substrate, precipitating the metal-organic framework material on the substrate, co-precipitating the metal-organic framework material on the substrate, dipping substrate in the metal-organic framework material, and coating the substrate with the metal-organic framework material.

8. The process according to claim 3, wherein the shaped body has at least one of the following features:

(i) the shaped body is in the form of a monolith,

(ii) the shaped body is in the form of a two-dimensional body,

(iii) the metal organic framework material is part of a wash-coat,

(iv) the shaped body has a skeleton-like or a honeycomb-like topology.

9. The process according to claim 6, wherein the shaped body has at least one of the following features:

(i) the shaped body is in the form of a monolith,

(ii) the shaped body is in the form of a two-dimensional body,

(iii) the metal organic framework material is part of a wash-coat,

(iv) the shaped body has a skeleton-like or a honeycomb-like topology.

10. A reaction comprising reacting reactants in the presence of the shaped body of claim 1, wherein said reacting is carried out in a fixed bed reactor, a packed bed reactor, or said shaped body is suspended in a slurry.

11. A catalyst comprising the shaped body of claim 1.

12. A catalyst support comprising the shaped body of claim 1.

13. A sorption material comprising the shaped body of claim 1.

14. A fluid storage material comprising the shaped body of claim 1.

15. A dessicant comprising the shaped body of claim 1.

16. An ion exchange material comprising the shaped body of claim 1.

17. A molecular sieve comprising the shaped body of claim 1.

18. A chromatography material comprising the shaped body of claim 1.

19. A selective release material comprising the shaped body of claim 1.

20. A material for absorbing or adsorbing molecules comprising the shaped body of claim 1.

21. A molecular recognition material comprising the shaped body of claim 1.

22. A nanotube comprising the shaped body of claim 1.

23. A nano-reactor comprising the shaped body of claim 1.