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.

Description

FIELD OF THE INVENTION[0001]This invention pertains to approaches for making molecular sieve / polymer mixed matrix membranes (MMMS) and methods for using these membranes. The MMMs prepared in the present invention comprising molecular sieves dispersed in a continuous polymer matrix exhibit a selectivity increase of at least 20% relative to a polymer membrane made from a continuous polymer matrix without molecular sieves.BACKGROUND OF THE INVENTION[0002]Gas separation processes using membranes have undergone a major evolution since the introduction of the first membrane-based industrial hydrogen separation process about two decades ago. The disclosure of new materials and efficient methods for making membranes will further advance the membrane gas separation processes within the next decade.[0003]The gas transport properties of many glassy and rubbery polymers have been measured as part of the search for materials with high permeability and high selectivity for potential use as gas se...

AI Technical Summary

Benefits of technology

[0010]The MMMs described in the current invention contain a thin dense selective permeable layer which comprises a continuous polymer matrix and discrete molecular sieve particles uniformly dispersed throughout the continuous polymer matrix. The molecular sieves in the MMMs can produce membranes having a selectivity and / or permeability that are significantly higher than the pure polymer membranes for separations. Addition of a small weight percent of molecular sieves to the polymer matrix, therefore, increases the overall separation efficiency significantly. The molecular sieves used in the MMMs of current invention include microporous and mesoporous molecular sieves, carbon molecular sieves, and porous metal-organic frameworks (MOFs). The microporous molecular sieves are selected from alumino-phosphate molecular sieves such as AlPO-18, AlPO-14, AlPO-53, and AlPO-17, aluminosilicate molecular sieves such as 4A, 5A, UZM-5, UZM-25, and UZM-9, silico-alumino-phosphate molecular sieves such as SAPO-34, and mixtures thereof. The continuous polymer matrix is selected from glassy polymers such as cellulose acetates, cellulose triacetates, polyimides, and polymers of intrinsic microporosity.

[0012]A membrane post-treatment step can be added after making the asymmetric hollow fiber MMM to improve selectivity without changing or damaging the membrane, or causing the membrane to lose performance with time. The membrane post-treatment step can involve coating the selective mixed matrix layer surface of the MMM with a thin layer of material such as a polysiloxane, a fluoro-polymer, a thermally curable silicone rubber, or a UV radiation curable silicone rubber. The asymmetric hollow fiber MMM made using this approach contains a thin dense selective mixed matrix layer on a porous non-selective pure polymer or mixed matrix layer.

[0014]The MMMs fabricated using the approaches described in the present invention combine the solution-diffusion mechanism of polymer membrane and the molecular sieving and sorption mechanism of molecular sieves, and assure maximum selectivity and consistent performance among different membrane samples comprising the same molecular sieve / polymer composition.

[0017]The MMMs of the present invention are suitable for a variety of liquid, gas, and vapor separations such as deep desulphurization of gasoline and diesel fuels, ethanol / water separations, pervaporation dehydration of aqueous / organic mixtures, CO2 / CH4, CO2 / N2, H2 / CH4, O2 / N2, olefin / paraffin, iso / normal paraffins separations, and other light gas mixture separations. The MMMs of the present invention have significantly improved selectivity and / or flux for these separations compared to the polymer membranes prepared from their corresponding continuous polymer matrices.

Problems solved by technology

Unfortunately, an important limitation in the development of new membranes for gas separation applications is a well-known trade-off between permeability and selectivity of polymers.

Despite concentrated efforts to tailor polymer structure to improve separation properties; current polymeric membrane materials have seemingly reached a limit in the trade-off between productivity and selectivity.

These polyimide and polyetherimide glassy polymers, however, do not have permeabilities attractive for commercialization compared to current commercial cellulose acetate membrane products.

On the other hand, some inorganic membranes, such as SAPO-34 and DDR zeolite membranes and carbon molecular sieve membranes, offer much higher permeability and selectivity than polymeric membranes for separations, but are too brittle, expensive, and difficult for large-scale manufacture.

This method, however, has a number of drawbacks including: 1) prohibitively expensive organosilicon coupling agents; 2) very complicated time consuming molecular sieve purification and organosilicon coupling agent recovery procedures after ftinctionalization.

Therefore, the cost of making such MMMs having organosilicon coupling agent functionalized molecular sieves in a commercially viable scale can be very expensive.

While the polymer “upper-bound” curve has been surpassed using solid / polymer MMMs, there are still many issues that need to be addressed for large-scale industrial production of these new types of MMMs.

Voids and defects, which result in reduced overall selectivity, are easily formed at the interface of the large molecular sieve particles and the thin polymer matrix of the asymmetric MMMs.