Molecular Sieve/Polymer Hollow Fiber Mixed Matrix Membranes

Abstract

The present invention discloses a method for making mixed matrix membranes (MMMs) and methods for using these membranes. These MMMs contain a continuous polymer matrix and dispersed microporous molecular sieve particles. This invention also pertains to control the thickness of the thin dense selective mixed matrix layer equal to or greater than the particle size of the largest molecular sieve particles for making large scale asymmetric MMMs. In particular, the invention is directed to make asymmetric hollow fiber MMM by a phase inversion technique. The MMMs of the present invention exhibit at least 20% increase in selectivity compared to the polymer membranes prepared from their corresponding continuous polymer matrices. The MMMs of the present invention are suitable for a variety of liquid, gas, and vapor separations.

1 . A process of making asymmetric hollow fiber mixed matrix membranes with at least 20% increase in selectivity compared to the asymmetric polymer membranes prepared from their corresponding polymer matrices, said process comprising:
 a) dispersing molecular sieve particles in an organic solvent or a mixture of two or more organic solvents to form a molecular sieve slurry;   b) dissolving a polymer or a blend of two polymers that serves as a continuous polymer matrix in the molecular sieve slurry;   c) adding one or more organic solvents that cannot dissolve the continuous polymer matrix to the molecular sieve slurry and stirring to form a stable molecular sieve/polymer spinning solution;   d) spinning hollow fiber mixed matrix membranes from the stable molecular sieve/polymer spinning solution using a hollow fiber spinning machine;   e) evaporating the organic solvents for a certain time by controlling the air gap to form a wet hollow fiber mixed matrix membrane with a thin dense selective mixed matrix layer with a thickness equal to or greater than the particle size of the largest molecular sieve particles on the surface;   f) dipping the wet hollow fiber mixed matrix membrane into a water bath to generate the porous non-selective pure polymer or mixed matrix membrane support layer below the thin dense selective mixed matrix top layer by phase inversion; and   g) washing and drying the asymmetric hollow fiber mixed matrix membrane.   
   
   
       2 . The process of  claim 1  comprising dissolving a second polymer in the molecular sieve slurry to functionalize the surface of molecular sieve particles; 
   
   
       3 . The process of  claim 1  wherein a coating is added to a top surface of said asymmetric hollow fiber mixed matrix membrane. 
   
   
       4 . The process of  claim 3  wherein said coating comprises a material selected from the group consisting of a polysiloxane, a fluoropolymer, a thermally curable silicone rubber and a UV radiation curable silicone polymer. 
   
   
       5 . The process of  claim 1  wherein said molecular sieve particles are characterized by a maximum diameter and said thin dense selective mixed matrix top layer is thicker than said maximum diameter. 
   
   
       6 . The process of  claim 2  wherein said second polymer is selected from the group consisting of polyethersulfones, sulfonated polyethersulfones, hydroxyl group-terminated poly(ethylene oxide)s, amino group-terminated poly(ethylene oxide)s, or isocyanate group-terminated poly(ethylene oxide)s, poly(esteramide-diisocyanate)s, hydroxyl group-terminated poly(propylene oxide)s, hydroxyl group-terminated co-block-poly(ethylene oxide)-poly(propylene oxide)s, hydroxyl group-terminated tri-block-poly(propylene oxide)-block-poly(ethylene oxide)-block-poly(propylene oxide)s, tri-block-poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), polyether ketones, poly(ethylene imine)s, poly(amidoamine)s, poly(vinyl alcohol)s, poly(allyl amine)s, poly(vinyl amine)s, and cellulosic polymers. 
   
   
       7 . The process of  claim 6  wherein said cellulosic polymers are selected from the group consisting of cellulose acetate, cellulose triacetate, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, and nitrocellulose. 
   
   
       8 . The process of  claim 2  wherein said second polymer is polyethersulfone. 
   
   
       9 . The process of  claim 1  wherein said polymer for said continuous polymer matrix is selected from the group consisting of polysulfones; polyetherimides; cellulosic polymers; polyamides; polyimides; polyamide/imides; polyether ketones; poly(ether ether ketone)s, poly(arylene oxides); poly(esteramide-diisocyanate); polyurethanes; poly(benzobenzimidazole)s; polyhydrazides; polyoxadiazoles; polytriazoles; poly(benzimidazole)s; polycarbodiimides; polybenzoxazoles; polyphosphazines; microporous polymers; and mixtures thereof. 
   
   
       10 . The process of  claim 1  wherein said polymer for said continuous polymer matrix is selected from the group consisting of polysulfone, polyetherimides, cellulose acetate, cellulose triacetate, polyamides, polyimides, P84 or P84HT, poly(3,3′,4,4′-benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-3,3′,5,5′-tetramethyl-4,4′-methylene dianiline), poly(3,3′,4,4′-benzophenone tetracarboxylic dianhydride-pyromellitic dianhydride-4,4′-oxydiphthalic anhydride-3,3′,5,5′-tetramethyl-4,4′-methylene dianiline), poly(3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride-3,3′,5,5′-tetramethyl-4,4′-methylene dianiline), poly(3,3′,4,4′-benzophenone tetracarboxylic dianhydride-3,3′,5,5′-tetramethyl-4,4′-methylene dianiline), poly(3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride-pyromellitic dianhydride-3,3′,5,5′-tetramethyl-4,4′-methylene dianiline), poly[2,2′-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-1,3-phenylenediamine], poly[2,2′-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-1,3-phenylenediamine-3,5-diaminobenzoic acid)], poly[2,2′-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane], poly(benzimidazole)s, polybenzoxazoles, and microporous polymers. 
   
   
       11 . The process of  claim 1  wherein said polymer for said continuous polymer matrix is selected from the group consisting of polyimides, polyetherimides, polyamides, cellulose acetate, cellulose triacetate, polybenzoxazoles, and microporous polymers. 
   
   
       12 . The process of  claim 1  wherein said molecular sieve is selected from the group consisting of microporous molecular sieves, mesoporous molecular sieves, carbon molecular sieves, and porous metal-organic frameworks. 
   
   
       13 . The process of  claim 12  wherein said microporous molecular sieves are small pore microporous molecular sieves selected from the group consisting of SAPO-34, Si-DDR, UZM-9, AlPO-14, AlPO-34, AlPO-17, AlPO-53, SSZ-62, SSZ-13, AlPO-18, UZM-25, ERS-12, CDS-1, MCM-65, MCM-47, 4A, 5A, UZM-5, UZM-9, SAPO-44, SAPO-47, SAPO-17, CVX-7, SAPO-35, SAPO-56, AlPO-52, SAPO-43; medium pore microporous molecular sieve silicalite-1; or large pore microporous molecular sieves selected from the group consisting of NaX, NaY, KY, CaY, and mixtures thereof. 
   
   
       14 . The process of  claim 1  wherein said mixed matrix membrane is used for a separation selected from the group consisting of deep desulfurization of gasoline or diesel fuels, ethanol/water separations, pervaporation dehydration of aqueous/organic mixtures, or gas separations. 
   
   
       15 . The process of  claim 1  wherein said gas separation comprises separating gases selected from the group consisting of CO 2 /CH 4 , CO 2 /N 2 , H 2 /CH 4 , O 2 /N 2 , olefin/paraffm (e.g. propylene/propane), iso/normal paraffins separations, and other light gas mixture separations.