Mixed matrix membranes incorporating surface-functionalized molecular sieve nanoparticles and methods for making the same

• US 7,846,496 B2
• Filed: 02/26/2007
• Issued: 12/07/2010
• Est. Priority Date: 03/10/2006
• Status: Active Grant

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: McCulloch, Beth, Liu, Chunqing, Wilson, Stephen T.
• Primary Examiner(s): Mulcahy; Peter D.
• Assistant Examiner(s): HU, HENRY S
• Application Number:
  US11/679,121
• Publication Number:
  US 20080039554A1
• Time in Patent Office: 1,380 Days
• Field of Search: 427/244, 427/216, 427/271, 427/273, 427/535, 96/4
• US Class Current: 427/244
• 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 71/0281 Zeolites
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

Mixed matrix membranes that are capable of separation and purification of gas mixtures are disclosed. These membranes comprise polymers that include dispersed therein nanomolecular sieve particles. In a preferred embodiment, the nanomolecular sieve particles contain attached functional groups to prevent their agglomeration.

Claims

1. A method of manufacturing a membrane comprising:

(a) selecting a quantity of one or more types of template-containing nano-molecular sieve particles;

(b) functionalizing template-containing nano-molecular sieve particles by an organic ligand-grafting-calcination-organic ligand-grafting method so as to obtain functionalized template-free nano-molecular sieve particles;

(c) forming a mixture by mixing 5 to 70 wt-% of said functionalized template-free nano-molecular sieve particles with a polymer; and

(d) casting a membrane from said mixture.

2. The method of claim 1 wherein said nano-molecular sieve particles have a particle size from 5 to 1000 nm.

3. The method of claim 1 wherein said nano-molecular sieve particles are selected from the group consisting of Si-MFI, SAPO-34, Si-MTW, Si-BEA, Si-MEL, LTA, FAU, Si-DDR, AlPO-14, AlPO-34, AlPO-18, AlPO-25, AlPO-5, SSZ-62, SSZ-13, UZM-9, UZM-25, CDS-1, MCM-65, Nu-6(2), and mixtures thereof.

4. The method of claim 1 wherein said polymer comprises at least one polymer selected from the group consisting of substituted and unsubstituted polymers and may be selected from polysulfones;

poly(styrenes), including styrene-containing copolymers comprising acrylonitrilestyrene copolymers, styrene-butadiene copolymers and styrene-vinylbenzylhalide copolymers;

polycarbonates;

cellulosic polymers, comprising cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose;

polyamides and polyimides, including aryl polyamides and aryl polyimides;

polyethers;

polyetherimides;

polyetherketones;

poly(arylene oxides) comprising poly(phenylene oxide) and poly(xylene oxide);

poly(esteramide-diisocyanate);

polyurethanes;

polyesters (including polyarylates), comprising poly(ethylene terephthalate), poly(alkyl methacrylates), poly(acrylates), poly(phenylene terephthalate);

polypyrrolones;

polysulfides;

polymers from monomers having alpha-olefinic unsaturation other than mentioned above comprising poly (ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls comprising poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl alcohol), poly(vinyl esters) comprising poly(vinyl acetate) and poly(vinyl propionate), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl ethers), poly(vinyl ketones), poly(vinyl aldehydes) comprising poly(vinyl formal) and poly(vinyl butyral), poly(vinyl amides), poly(vinyl amines), poly(vinyl urethanes), poly(vinyl ureas), poly(vinyl phosphonates), and poly(vinyl sulfonates);

polyallyls;

poly(benzobenzimidazole);

polyhydrazides;

polyoxadiazoles;

polytriazoles;

poly (benzimidazole);

polycarbodiimides;

polyphosphazines; and

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

grafts and blends containing any of the foregoing, wherein typical substituents providing substituted polymers include halogens comprising fluorine, chlorine and bromine;

hydroxyl groups;

lower alkyl groups;

lower alkoxy groups;

monocyclic aryl; and

lower acid groups.

5. The method of claim 1 wherein said polymer comprises at least one polymer selected from the group consisting of cellulose acetate, cellulose triacetate, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, cellulose nitrate, polyurethane, polycarbonate, and polystyrene.

6. The method of claim 1 wherein said functionalizing template-free nano-molecular sieve particles comprises grafting functional organic linkages on a surface of said nano-molecular sieve particles.

7. The method of claim 6 wherein said functional organic linkage is an organosilane.

8. The method of claim 7 wherein said functional organosilane linkage is a compound having the formula R(CH₂)_nSi(OR₁)₃ in which R is a functional group selected from the group consisting of 4,5-dihydroimidazole, poly(ethylene glycol), SH, NH₂, C≡

N, O═

C═

N, OH, NH(CH₂)₂NH₂, OCH₂CH(OH)CH₂N(CH₂CH₂OH)₂, calix[n]arenes (n=4, 6, or

     8), or R is an ionic group selected from the group consisting of N⁺CH₃((CH₂)₉CH₃)₂Cl⁻

, N⁺((CH₂)₁₇CH₃)(CH₃)₂Cl, N⁺(CH₃)₃Cl⁻

, N⁺(CH₂CH₃)₃Cl⁻

, N⁺(CH₂CH₂CH₂CH₃)₃Cl⁻

and other trialkyl ammonium groups, n is an integer from 1 to 20, and R₁ is a C₁-C₈ hydrocarbon group.

9. The method of claim 7 wherein said functional organic linkage is a compound having the formula R(CH₂)_nSiR′

(OR¹)₂ in which R is an organic functional group selected from the group consisting of 4,5-dihydroimidazole, poly(ethylene glycol), SH, NH₂, C≡

N, O═

C═

N, OH, NH(CH₂)₂NH₂, OCH₂CH(OH)CH₂N(CH₂CH₂OH)₂, calix[n]arenes (n=4, 6, or

     8), or R is an ionic group selected from the group consisting of N⁺CH₃((CH₂)₉CH₃)₂Cl⁻

, N⁺((CH₂)₁₇CH₃)(CH₃)₂Cl, N⁺(CH₃)₃Cl⁻

, N⁺(CH₂CH₃)₃Cl⁻

, N⁺(CH₂CH₂CH₂CH₃)₃Cl⁻

and other trialkyl ammonium groups, n is an integer from 1 to 20, R₁ is a C₁-C₈ hydrocarbon group, and R′

is a C₁-C₈ hydrocarbon group.

10. The method of claim 7 wherein said functional organic linkage is a compound having the formula R(CH₂)_nSiR′

(R″

)(OR₁) in which R is an organic functional group selected from the group consisting of 4,5-dihydroimidazole, poly(ethylene glycol), SH, NH₂, C≡

N, O═

C═

N, OH, NH(CH₂)₂NH₂, OCH₂CH(OH)CH₂N(CH₂CH₂OH)₂, calix[n]arenes (n=4, 6, or

     8), or R is an ionic group selected from the group consisting of N⁺CH₃((CH₂)₉CH₃)₂Cl⁻

, N⁺((CH₂)₁₇CH₃)(CH₃)₂Cl⁻

, N⁺(CH₃)₃Cl⁻

, N⁺(CH₂CH₃)₃Cl⁻

, N⁺(CH₂CH₂CH₂CH₃)₃Cl⁻

and other trialkyl ammonium groups, n is an integer from 1 to 20, R₁ is a C₁-C₈ hydrocarbon group, R′

is a C₁-C₈ hydrocarbon group, and R″

is a C₁-C₈ hydrocarbon group.

11. The method of claim 1 wherein said nano-molecular sieve initially contains a structure-directing template and wherein after the grafting of said functional group to said nano-molecular sieve, said structure-directing template is removed from said nano-molecular sieve by calcination.

12. The method of claim 11 further comprising a second grafting step wherein following said calcination, a second organosilane compound is grafted to said calcinated nano-molecular sieve to form functionalized template-free molecular sieve nanoparticles.

13. The method of claim 12 wherein said second organosilane comprises a compound having the formula R₂ (CH₂)_mSi(OR₃)₃ wherein R₂ is a functional group selected from the group consisting of 4,5-dihydroimidazole, poly(ethylene glycol), SH, NH₂, C≡

N, O═

C═

N, OH, NH(CH₂)₂NH₂, OCH₂CH(OH)CH₂N(CH₂CH₂OH)₂, calix[n]arenes (n=4, 6, or

     8), or R an ionic group selected from the group consisting of N⁺CH₃((CH₂)₉CH₃)₂Cl⁻

, N⁺((CH₂)₁₇CH₃)(CH₃)₂Cl, N⁺(CH₃)₃Cl⁻

, N⁺(CH₂CH₃)₃Cl⁻

, N⁺(CH₂CH₂CH₂CH₃)₃Cl⁻

and other trialkyl ammonium groups, m is an integer from 1 to 20, and R₃ is a C₁-C₈ hydrocarbon group, and R, R₁, R₂, R₃, m, n are each independent.

14. The method of claim 12 wherein said second organosilane comprises a compound having the formula R(CH₂)_nSiR′

(OR¹)₂ in which R is an organic functional group selected from the group consisting of 4,5-dihydroimidazole, poly(ethylene glycol), SH, NH₂, C≡

N, O═

C═

N, OH, NH(CH₂)₂NH₂, OCH₂CH(OH)CH₂N(CH₂CH₂OH)₂, calix[n]arenes (n=4, 6, or

     8), or R is an ionic group selected from the group consisting of N⁺CH₃((CH₂)₉CH₃)₂Cl⁻

, N⁺((CH₂)₁₇CH₃)(CH₃)₂Cl, N⁺(CH₃)₃Cl⁻

, N⁺(CH₂CH₃)₃Cl⁻

, N⁺(CH₂CH₂CH₂CH₃)₃Cl⁻

and other trialkyl ammonium groups, n is an integer from 1 to 20, R₁ is a C₁-C₈ hydrocarbon group, and R′

is a C₁-C₈ hydrocarbon group.

15. The method of claim 12 wherein said second organosilane comprises a compound having the formula R(CH₂)_nSiR′

(R″

)(OR₁) in which R is an organic functional group selected from the group consisting of 4,5-dihydroimidazole, poly(ethylene glycol), SH, NH₂, C≡

N, O═

C═

N, OH, NH(CH₂)₂NH₂, OCH₂CH(OH)CH₂N(CH₂CH₂OH)₂, calix[n]arenes (n=4, 6, or

     8), or R is an ionic group selected from the group consisting of N⁺CH₃((CH₂)₉CH₃)₂Cl⁻

, N⁺((CH₂)₁₇CH₃)(CH₃)₂Cl, N⁺(CH₃)₃Cl⁻

, N⁺(CH₂CH₃)₃Cl⁻

, N⁺(CH₂CH₂CH₂CH₃)₃Cl⁻

and other trialkyl ammonium groups, n is an integer from 1 to 20, R₁ is a C₁-C₈ hydrocarbon group, R′

is a C₁-C₈ hydrocarbon group, and R″

is a C₁-C₈ hydrocarbon group.

16. The method of claim 12 wherein said functionalized template-free molecular sieve nanoparticles are dispersible in organic solvents.

17. A mixed matrix membrane made by the method of claim 1.