Method of making high performance mixed matrix membranes using suspensions containing polymers and polymer stabilized molecular sieves

• US 7,815,712 B2
• Filed: 12/18/2006
• Issued: 10/19/2010
• Est. Priority Date: 12/18/2006
• Status: Active Grant

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Lesch, David A., Tang, Man-Wing, Liu, Chunqing, Wilson, Stephen T.
• Primary Examiner(s): Greene; Jason M
• Application Number:
  US11/612,366
• Publication Number:
  US 20080141863A1
• Time in Patent Office: 1,401 Days
• Field of Search: 96/4, 96/8, 96/10, 96/11, 96/12, 96/13, 96/14, 95/45, 95/51, 95/52, 95/54, 95/55, 210/640, 210/641, 210/500.27, 210/502.1, 555/23, 555/24, 55D/IG.5
• US Class Current: 95/45
• CPC Class Codes: B01D 2323/21 Fillers
• CPC Class Codes: B01D 61/362 Pervaporation
• 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 71/028 Molecular sieves carbon B01D71/021
• CPC Class Codes: B01D 71/0281 Zeolites
• CPC Class Codes: Y10S 55/05 Methods of making filter

Abstract

The present invention discloses a novel method of making high performance mixed matrix membranes (MMMs) using stabilized concentrated suspensions of solvents, uniformly dispersed polymer stabilized molecular sieves, and at least two different types of polymers as the continuous blend polymer matrix. MMMs as dense films or asymmetric flat sheet or hollow fiber membranes fabricated by the method described in the current invention exhibit significantly enhanced permeation performance for separations over the polymer membranes made from the continuous blend polymer matrix. MMMs of the present invention are suitable for a wide range of gas, vapor, and liquid separations such as alcohol/water, CO₂/CH₄, H₂/CH₄, O₂/N₂, CO₂/N₂, olefin/paraffin, iso/normal paraffins, and other light gases separations.

Claims

1. A mixed matrix membrane comprising a dispersion of polymer stabilized molecular sieves in a continuous polymer matrix wherein said molecular sieves are stabilized by a composition consisting essentially of at least one glassy polymer wherein said polymer is a hydroxyl or amino group-terminated polymer selected from the group consisting of polyethersulfones, sulfonated polyethersulfones, polyethers, polyether ketones, poly(ethylene imine)s, poly(amidoamine)s, and polyetherimides or said polymer is a hydroxyl group-containing glassy polymer selected from the group consisting of poly(vinyl alcohol)s, cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose, and wherein said continuous polymer matrix comprises at least two different glassy polymers.

2. The mixed matrix membrane of claim 1 wherein said molecular sieves are selected from the group consisting of nano-molecular sieves, microporous molecular sieves, mesoporous molecular sieves, carbon molecular sieves, and porous metal-organic frameworks.

3. The mixed matrix membrane of claim 1 wherein the ratio of said molecular sieves to said polymer to stabilize said molecular sieves is between about 5 parts molecular sieve by weight to 100 parts polymer by weight and 100 parts molecular sieves by weight to 1 part polymer by weight.

4. The mixed matrix membrane of claim 1 wherein said at least two different polymers are selected from the group consisting of polysulfones, sulfonated polysulfones;

polyethersulfones, sulfonated polyethersulfones, polyethers, polyetherimides;

poly(styrenes);

styrene-containing copolymers selected from the group consisting of acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers;

polycarbonates;

cellulosic polymers selected from the group consisting of as cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose;

polyamides;

polyimides;

polyamide/imides;

polyketones, polyether ketones;

poly(arylene oxides);

poly(phenylene oxide) and poly(xylene oxide);

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;

microporous polymers;

interpolymers, block interpolymers containing repeating units from the above said polymers as terpolymers of acrylonitrile-vinyl bromide-sodium salt of para-sulfophenylmethallyl ethers; and

grafts and blends of said polymers.

5. The mixed matrix membrane of claim 1 wherein said at least two different polymers are selected from the group consisting of polysulfones, sulfonated polysulfones, polyethersulfones (PESs), sulfonated PESs, polyethers, polyetherimides, cellulosic polymers wherein said cellulosic polymers are cellulose acetate or cellulose triacetate;

polyamides;

polyimides, poly(3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(BTDA-PMDA-TMMDA)), poly(3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-4,4′

-oxydiphthalic anhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(BTDA-PMDA-ODPA-TMMDA)), poly(3,3′

,4,4′

-diphenylsulfone tetracarboxylic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(DSDA-TMMDA)), poly(3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(BTDA-TMMDA)), poly(3,3′

,4,4′

-diphenylsulfone tetracarboxylic dianhydride-pyromellitic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(DSDA-PMDA-TMMDA)), poly[2,2′

-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-1,3-phenylenediamine](poly(6FDA-m-PDA)), poly[2,2′

-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-1,3-phenylenediamine-3,5-diaminobenzoic acid)](poly(6FDA-m-PDA-DABA)), polyamide/imides mixtures;

polyketones, polyether ketones; and

microporous polymers.

6. The mixed matrix membrane of claim 1 wherein said polymer in said polymer stabilized molecular sieve is the same as one of said at least two different polymers in said polymer matrix.

7. The mixed matrix membrane of claim 1 wherein said polymer in said polymer stabilized molecular sieve is different from either of said at least two different polymers in said polymer matrix.

8. The mixed matrix membrane of claim 1 wherein said mixed matrix membrane is a dense film mixed matrix membrane or an asymmetric flat sheet or hollow fiber mixed matrix membrane.

9. The mixed matrix membrane of claim 2 wherein said nano-molecular sieves comprise particles between 5 to 1000 nm in size wherein said nano-molecular sieves are selected from the group consisting of silicalite-1, SAPO-34, Si-MTW, Si-BEA, Si-MEL, LTA, FAU, Si-DDR, AlPO-14, AlPO-34, AlPO-18, SSZ-62, UZM-5, UZM-9, UZM-13, UZM-17, UZM-19, and MCM-65.

10. The mixed matrix membrane of claim 2 wherein said microporous molecular sieves are selected from the group consisting of aluminophosphates, silicoaluminophosphates, metalloaluminophosphates, elemental aluminophosphates, metallosilicoaluminophosphates and elemental silicoaluminophosphates.

11. The mixed matrix membrane of claim 2 wherein the ratio of molecular sieve to continuous polymer matrix is between 1:

100 to 100;

100.

12. The mixed matrix membrane of claim 1 further comprising a coating selected from the group consisting of polysiloxane, a thermally curable silicon rubber and a UV radiation curable epoxy silicon.

13. A method of making a mixed matrix membrane comprising:

a) dispersing a composition consisting essentially of molecular sieve particles in at least one solvent to form a slurry;

b) then dissolving a glassy polymer to stabilize said molecular sieve particles in said slurry to form a polymer stabilized molecular sieve slurry wherein said polymer is a hydroxyl or amino group-terminated polymer selected from the group consisting of polyethersulfones, sulfonated polyethersulfones, polyethers, polyether ketones, poly(ethylene imine)s, poly(amidoamine)s, and polyetherimides or is a hydroxyl group-containing glassy polymer selected from the group consisting of poly(vinyl alcohol)s, cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose;

c) then dissolving and mixing two glassy polymers into said polymer stabilized molecular sieve slurry to form a stabilized concentrated suspension; and

d) then fabricating a mixed matrix membrane from said stabilized concentrated suspension.

14. The method of claim 13 further comprising applying a coating to said mixed matrix membrane.

15. The method of claim 14 wherein said coating is selected from the group consisting of polysiloxane, a thermally curable silicon rubber, and a UV radiation curable epoxy silicon.

16. The method of claim 13 wherein said mixed matrix membrane is a dense film or an asymmetric flat sheet or hollow fiber membrane.

17. The method of claim 13 wherein said molecular sieves are selected from the group consisting of nano-molecular sieves, microporous molecular sieves, mesoporous molecular sieves, carbon molecular sieves and porous metal-organic frameworks.

18. The method of claim 13 wherein said two polymers are selected from the group consisting of polysulfones, sulfonated polysulfones;

polyethersulfones, sulfonated polyethersulfones, polyethers, polyetherimides;

poly(styrenes);

styrene-containing copolymers selected from the group consisting of acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers;

polycarbonates;

cellulosic polymers selected from the group consisting of as cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose;

polyamides;

polyimides;

polyamide/imides;

polyketones, polyether ketones;

poly(arylene oxides);

poly(phenylene oxide) and poly(xylene oxide);

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;

microporous polymers;

interpolymers, block interpolymers containing repeating units from the above said polymers as terpolymers of acrylonitrile-vinyl bromide-sodium salt of para-sulfophenylmethallyl ethers; and

grafts and blends of said polymers.

19. The method of claim 13 wherein said at least two different polymers are selected from the group consisting of polysulfones, sulfonated polysulfones, polyethersulfones (PESs), sulfonated PESs, polyethers, polyetherimides, cellulosic polymers wherein said cellulosic polymers are cellulose acetate or cellulose triacetate;

polyamides;

polyimides, poly(3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(BTDA-PMDA-TMMDA)), poly(3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-4,4′

-oxydiphthalic anhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(BTDA-PMDA-ODPA-TMMDA)), poly(3,3′

,4,4′

-diphenylsulfone tetracarboxylic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(DSDA-TMMDA)), poly(3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(BTDA-TMMDA)), poly(3,3′

,4,4′

-diphenylsulfone tetracarboxylic dianhydride-pyromellitic dianhydride-3,3′

,5,5′

-tetramethyl-4,4′

-methylene dianiline) (poly(DSDA-PMDA-TMMDA)), poly[2,2′

-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-1,3-phenylenediamine](poly(6FDA-m-PDA)), poly[2,2′

-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-1,3-phenylenediamine-3,5-diaminobenzoic acid)](poly(6FDA-m-PDA-DABA)), P84 or P84HT;

polyamide/imides mixtures;

polyketones, polyether ketones; and

microporous polymers.

20. The method of claim 13 wherein said polymer in said polymer stabilized molecular sieve is the same as one of said at least two different polymers in said polymer matrix.

21. The method of claim 13 wherein said polymer in said polymer stabilized molecular sieve is different from either of said at least two different polymers in said polymer matrix.

22. The method of claim 13 wherein said solvent is at least one solvent selected from the group consisting of amide solvents, methylene chloride, THF, acetone, DMF, DMSO, toluene, dioxanes, and 1,3-dioxolane.

23. The method of claim 22 wherein said amide solvents are N-methylpyrrolidone (NMP) or N,N-dimethyl acetamide.

24. The method of claim 13 wherein said mixed matrix membrane is a dense film mixed matrix membrane or an asymmetric flat sheet or hollow fiber mixed matrix membrane.

25. The method of claim 17 wherein said nano-molecular sieves comprise particles between 5 to 1000 nm in size wherein said nano-molecular sieves are selected from the group consisting of silicalite-1, SAPO-34, Si-MTW, Si-BEA, Si-MEL, LTA, FAU, Si-DDR, AlPO-14, AlPO-34, AlPO-18, SSZ-62, UZM-5, UZM-9, UZM-13, UZM-17, UZM-19, and MCM-65.

26. The method of claim 17 wherein said microporous molecular sieves are selected from the group consisting of aluminophosphates, silicoaluminophosphates, metalloaluminophosphates, elemental aluminophosphates, metallosilicoaluminophosphates and elemental silicoaluminophosphates.