Metal organic framework—polymer mixed matrix membranes

• US 7,637,983 B1
• Filed: 06/30/2006
• Issued: 12/29/2009
• Est. Priority Date: 06/30/2006
• Status: Expired due to Fees

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Liu, Chunqing, Wilson, Stephen T., Schott, Mark E., Benin, Annabelle I., McCulloch, Beth
• Primary Examiner(s): Greene; Jason M
• Application Number:
  US11/427,834
• Time in Patent Office: 1,278 Days
• Field of Search: 95/45, 95/50, 95/51, 95/54, 95/55, 96/4, 96/11, 96/12, 96/13, 96/14, 210/640, 210/500.21, 210/500.27
• US Class Current: 95/45
• CPC Class Codes: B01D 2253/204 Metal organic frameworks (MOF's)
• 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 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0079 Manufacture of membranes comprising organic and inorganic components
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 69/148 Organic/inorganic mixed matrix membranes
• CPC Class Codes: B01D 71/00 Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
• CPC Class Codes: B01D 71/56 Polyamides, e.g. polyester-amides
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/643 Polyether-imides
• CPC Class Codes: B01J 20/22 comprising organic material
• 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 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/28026 Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: B01J 2220/44 Materials comprising a mixture of organic materials materials coated or impregnated on a carrier B01J20/32

Abstract

Metal-organic framework (MOF)-polymer mixed matrix membranes (MOF-MMMs) have been prepared by dispersing high surface area MOFs (e.g. IRMOF-1) into a polymer matrix (e.g. Matrimid 5218). The MOFs allow the polymer to infiltrate the pores of the MOFs, which improves the interfacial and mechanical properties of the polymer and in turn affects permeability. Pure gas permeation tests show the incorporation of 20 wt-% of IRMOF-1 in Matrimid 5218 polyimide matrix results in 280% improvement in CO₂ permeability without a loss of CO₂/CH₄ selectivity compared to those of the pure Matrimid 5218 membrane. This type of MOF-MMMs has significantly improved gas separation performance with dramatically high CO₂ permeability (>35 barrer) and higher than 29 CO₂/CH₄ selectivity at 50° C. under 100 psig pressure, which are attractive candidates for practical gas separation applications such as CO₂ removal from natural gas.

Claims

1. A process for separating at least one gas from a mixture of gases, the process comprising:

a) providing a mixed matrix gas separation membrane comprising a metal organic framework (MOF) material dispersed in a continuous phase consisting essentially of a polymer which is permeable to said at least one gas;

b) contacting the mixture on one side of the mixed matrix membrane to cause said at least one gas to permeate the mixed matrix membrane; and

c) removing from the opposite side of the membrane a permeate gas composition comprising a portion of said at least one gas which permeated said membrane.

2. The process of claim 1 wherein said MOF comprises a systematically formed metal-organic framework having a plurality of metal, metal oxide, metal cluster or metal oxide cluster building units, and an organic compound linking adjacent building units, wherein the linking compound comprises a linear dicarboxylate having at least one substituted phenyl group.

3. The process of claim 2 wherein the MOFs are selected from the group consisting of MOF-5, a material having a general formula of Zn₄O(1,4-benzenedicarboxylate)₃;

IRMOF-6, a material having a general formula of Zn₄O(cyclobutyl 1,4-benzenedicarboxylate);

IRMOF-3, a material having a general formula of Zn₄O(2-amino 1,4 benzenedicarboxylate)₃; and

IRMOF-11, a material having a general formula of Zn₄O(terphenyl dicarboxylate)₃, or Zn₄O(tetrahydropyrene 2,7-dicarboxylate)₃;

IRMOF-8, a material having a general formula of Zn₄O(2,6 naphthalene dicarboxylate)₃, and mixtures thereof.

4. The process of claim 2 wherein the MOF is MOF-5 and has a general formula of Zn₄O(1,4-benzenedicarboxylate)₃ with a three-dimensional extended porous structure.

5. The process of claim 2 wherein the MOF is MOF-177 and has a general formula of Zn₄O(1,3,5-benzenetribenzoate)₃ with a three-dimensional extended porous structure.

6. The process of claim 1 wherein said continuous phase comprises one or more polymers selected from the group consisting of polysulfones;

poly(styrenes), styrene-containing copolymers, polycarbonates;

cellulosic polymers, polyimides, polyetherimides, and polyamides, aryl polyamides, aryl polyimides, aryl polyetherimides;

polyethers;

poly(arylene oxides);

poly(esteramide-diisocyanate);

polyurethanes;

polyesters, polysulfides;

poly(ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls, polyallyls;

poly(benzobenzimidazole);

polyhydrazides;

polyoxadiazoles;

polytriazoles;

poly(benzimidazole);

polycarbodiimides;

polyphosphazines;

etc., and interpolymers, including block interpolymers containing repeating units from the above polymers.

7. The process of claim 6 wherein said continuous phase comprises one or more polymers selected from the group consisting of polyimides, polyetherimides, and polyamides.

8. The process of claim 1 wherein said mixture of gases comprises a pair of gases selected from the group consisting of hydrogen/methane, carbon dioxide/methane, carbon dioxide/nitrogen, oxygen/nitrogen, methane/nitrogen and olefin/paraffin.

9. A mixed matrix membrane comprising a continuous phase organic polymer and an MOF dispersed in said continuous phase organic polymer.

10. The mixed matrix membrane of claim 9 wherein said MOF comprises a systematically formed metal-organic framework having a plurality of metal, metal oxide, metal cluster or metal oxide cluster building units, and an organic compound linking adjacent building units, wherein the linking compound comprises a linear dicarboxylate having at least one substituted phenyl group.

11. The mixed matrix membrane of claim 10 wherein the MOFs are selected from the group consisting of MOF-5, a material having a general formula of Zn₄O(1,4-benzenedicarboxylate)₃;

IRMOF-6, a material having a general formula of Zn₄O(cyclobutyl 1,4-benzenedicarboxylate);

IRMOF-3, a material having a general formula of Zn₄O(2-amino 1,4 benzenedicarboxylate)₃; and

IRMOF-11, a material having a general formula of Zn₄O(terphenyl dicarboxylate)₃, or Zn₄O(tetrahydropyrene 2,7-dicarboxylate)₃;

IRMOF-8, a material having a general formula of Zn₄O(2,6 naphthalene dicarboxylate)₃, and mixtures thereof.

12. The mixed matrix membrane of claim 9 wherein the MOF is MOF-5 and has a general formula of Zn₄O(1,4-benzenedicarboxylate)₃ with a three-dimensional extended porous structure.

13. The mixed matrix membrane of claim 9 wherein the MOF is MOF-177 and has a general formula of Zn₄O(1,3,5-benzenetribenzoate)₃ with a three-dimensional extended porous structure.

14. The mixed matrix membrane of claim 9 wherein said continuous phase comprises one or more polymers selected from the group consisting of polysulfones;

poly(styrenes), styrene-containing copolymers, polycarbonates;

cellulosic polymers, polyimides, polyetherimides, and polyamides, aryl polyamides, aryl polyimides, aryl polyetherimides;

polyethers;

poly(arylene oxides);

poly(esteramide-diisocyanate);

polyurethanes;

polyesters, polysulfides;

poly(ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls, polyallyls;

poly(benzobenzimidazole);

polyhydrazides;

polyoxadiazoles;

polytriazoles;

poly(benzimidazole);

polycarbodiimides;

polyphosphazines;

etc., and interpolymers, including block interpolymers containing repeating units from the above polymers.

15. The mixed matrix membrane of claim 9 wherein said continuous phase comprises one or more polymers selected from the group consisting of polyimides, polyetherimides, and polyamides.

16. A process for preparation of a mixed matrix membrane comprising:

a) forming a polymer solution by mixing a polymer selected from the group consisting of polysulfones;

poly(styrenes), styrene-containing copolymers, polycarbonates;

cellulosic polymers, polyimides, polyetherimides, and polyamides, aryl polyamides, aryl polyimides, aryl polyetherimides;

polyethers;

poly(arylene oxides);

poly(esteramide-diisocyanate);

polyurethanes;

polyesters, polysulfides;

poly(ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls, polyallyls;

poly(benzobenzimidazole);

polyhydrazides;

polyoxadiazoles;

polytriazoles;

poly(benzimidazole);

polycarbodiimides;

polyphosphazines;

etc., and interpolymers, including block interpolymers containing repeating units from the above polymers with a solvent;

b) forming an MOF-polymer slurry by mixing said polymer solution with at least one MOF comprising a systematically formed metal-organic framework having a plurality of metal, metal oxide, metal cluster or metal oxide cluster building units, and an organic compound linking adjacent building units, wherein the linking compound comprises a linear dicarboxylate having at least one substituted phenyl group; and

c) casting said MOF-polymer slurry as a thin layer upon a substrate followed by evaporating the solvents in the thin layer, or followed by evaporating the solvents in the thin layer and then immersing the thin layer into a coagulation bath to form an MOF-polymer mixed matrix membrane.

17. The process of claim 16 wherein said polymer is selected from the group consisting of polyimides, polyetherimides, and polyamides.