# US 8,540,800 B2 · Microporous UZM-5 inorganic zeolite membranes for gas, vapor, and liquid separations

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 8,540,800 B2
- Document ID: US8540800B2
- Status: Granted
- Kind: B2
- Application number: 13/052,720
- Filed: 2011-03-21
- Published: 2012-09-27
- Granted: 2013-09-24
- Earliest claimed: 2011-03-21
- Assignees: Uop LLC
- Applicants: Chunqing Liu; Jaime G. Moscoso; Stephen T. Wilson
- Inventors: Chunqing Liu; Jaime G. Moscoso; Stephen T. Wilson
- Web page: https://patentgrep.com/patent/US8540800B2

## CPC

- B01D 71/0281: {Zeolites}
- B01D 53/228: {characterised by specific membranes}
- B01D 67/0048: {by sol-gel transition}
- B01D 67/0051: {by controlled crystallisation, e,.g. hydrothermal growth}
- B01D 67/0088: {Physical treatment with compounds, e.g. swelling, coating or impregnation}
- B01D 69/10: Supported membranes; Membrane supports
- B01J 20/186: {Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity}
- B01J 20/28007: {with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like (carbon nanostructures B01J20/205)}
- B01J 20/28035: {with more than one layer, e.g. laminates, separated sheets}
- B01J 20/3057: {Use of a templating or imprinting material (molecularly imprinted polymers B01J20/268); filling pores of a substrate or matrix followed by the removal of the substrate or matrix}
- B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01J 20/3238: {containing any type of zeolite}
- B01J 20/3272: {Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B01D 2323/14: Ageing features
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

The present invention discloses microporous UZM-5 zeolite membranes, methods for making the same, and methods of separating gases, vapors, and liquids using the same. The small-pore microporous UZM-5 zeolite membrane is prepared by two different methods, including in-situ crystallization of one or more layers of UZM-5 zeolite crystals on a porous membrane support, and a seeding method by in-situ crystallization of a continuous second layer of UZM-5 zeolite crystals on a seed layer of UZM-5 zeolite crystals supported on a porous membrane support. The membranes in the form of disks, tubes, or hollow fibers have superior thermal and chemical stability, good erosion resistance, high CO2 plasticization resistance, and significantly improved selectivity over polymer membranes for gas, vapor, and liquid separations.

## Claims

### Claim 1

A method for making a microporous inorganic UZM-5 zeolite membrane by in-situ crystallization of a continuous single layer or continuous multiple layers of UZM-5 zeolite crystals on a porous membrane support comprising the steps of:
(a) providing a porous inorganic membrane support;
(b) synthesizing an aqueous UZM-5 zeolite-forming gel by combining reactive sources of R, aluminum (Al), optionally E and/or M and silicon (Si) in aqueous media wherein the composition of R, Al, E, M, Si, and O in terms of mole ratios of the elements is:
Mmn+Rrp+Al(1-x)ExSiyOz
where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, “m” is the mole ratio of M to (Al+E) and varies from 0 to about 1.2, R is a nitrogen-containing organic cation selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, diquaternaryammonium ions, quaternized alkanolamines and mixtures thereof, “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 3.0, E is at least one element selected from the group consisting of Ga, Fe, Cr, In and B, “x” is the mole fraction of E and varies from 0 to about 0.5, “n” is the weighted average valence of M and has a value of about +1 to about +2, “p” is the weighted average valence of R and has a value of +1 to about +2, “y” is the mole ratio of Si to (Al+E) and varies from about 5 to about 12 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m•n+r•p+3+4•y)/2;
(c) aging the UZM-5 zeolite-forming gel at 25° to 100° C. for 1 to 120 hours to produce an aged UZM-5 zeolite-forming gel;
(d) contacting at least one surface of the porous inorganic membrane support with the aged UZM-5 zeolite-forming gel;
(e) heating the porous inorganic membrane support and the aged UZM-5 zeolite-forming gel to form a continuous layer of UZM-5 zeolite crystals on at least one surface of the porous inorganic membrane support or inside the pores of the porous inorganic membrane support to produce a UZM-5 zeolite membrane;
(f) calcining the resulting inorganic UZM-5 zeolite membrane at high temperature in a range of 400° to 600° C. to form a microporous inorganic UZM-5 zeolite membrane; and
(g) coating the whole surface or part of the surface of said layer of UZM-5 zeolite crystals of the said microporous inorganic UZM-5 zeolite membrane with a thin layer of high flux polymer material selected from the group consisting of a polydimethylsiloxane (PDMS), a polybenzoxazole, a polymer with intrinsic microporosity, or a mixture thereof;
wherein the microporous inorganic UZM-5 zeolite membrane comprises at least 95% UZM-5 zeolites.

### Claim 2 (depends on 1)

The method of claim 1 further comprising contacting the UZM-5 zeolite membrane obtained in step (e) with the said aged UZM-5 zeolite-forming gel again and repeating steps (d) to (e) at least twice.

### Claim 3 (depends on 1)

The method of claim 1 wherein said porous inorganic membrane support comprises pores having an average pore size of 0.1-1 μm.

### Claim 4 (depends on 1)

The method of claim 1 wherein said microporous inorganic UZM-5 zeolite membrane is in a form selected from the group consisting of disk, tube and hollow fiber.

### Claim 5

A method for making a microporous inorganic UZM-5 zeolite membrane comprising
(a) providing a porous inorganic membrane support having an average pore size of 0.1-1 μm;
(b) providing UZM-5 zeolite seeds in the as synthesized form with an average particle size of about 10 nm to 2 μm;
(c) dispersing the UZM-5 zeolite seed particles in the as synthesized form in a solvent to prepare a colloidal solution of the UZM-5 zeolite seed particles;
(d) coating a layer of the colloidal solution of the UZM-5 zeolite seed particles on at least one surface of the porous inorganic membrane support;
(e) drying the colloidal solution layer of the UZM-5 zeolite seed particles on the surface of the porous inorganic membrane support to form a seed layer of UZM-5 zeolite crystals on the porous inorganic membrane support;
(f) synthesizing an aqueous UZM-5 zeolite-forming gel by combining reactive sources of R, aluminum (Al), optionally E and/or M and silicon (Si) in aqueous media wherein the composition of R, Al, E, M, Si, and O in terms of mole ratios of the elements is:
Mmn+Rrp+Al(1-x)ExSiyOz
where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, “m” is the mole ratio of M to (Al+E) and varies from 0 to about 1.2, R is a nitrogen-containing organic cation selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, diquaternaryammonium ions, quaternized alkanolamines and mixtures thereof, “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 3.0, E is at least one element selected from the group consisting of Ga, Fe, Cr, In and B, “x” is the mole fraction of E and varies from 0 to about 0.5, “n” is the weighted average valence of M and has a value of about +1 to about +2, “p” is the weighted average valence of R and has a value of +1 to about +2, “y” is the mole ratio of Si to (Al+E) and varies from about 5 to about 12 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m•n+r•p+3+4•y)/2;
(g) aging the UZM-5 zeolite-forming gel at 25° to 100° C. for 1 to 120 hours to produce an aged UZM-5 zeolite-forming gel;
(h) contacting the surface of the seed layer of UZM-5 zeolite crystals supported on a porous inorganic membrane support with the aged UZM-5 zeolite-forming gel;
(i) heating the seeded porous inorganic membrane support and the aged UZM-5 zeolite-forming gel to form a continuous second layer of inorganic UZM-5 zeolite crystals on the seed layer of UZM-5 zeolite crystals supported on the porous inorganic membrane support;
(j) calcining the resulting dual layer inorganic UZM-5 zeolite membrane at high temperature in a range of 400° to 600° C. to form a microporous inorganic UZM-5 zeolite membrane; and
(k) coating the whole surface or part of the surface of said layer of UZM-5 zeolite crystals of the said microporous inorganic UZM-5 zeolite membrane with a thin layer of high flux polymer material selected from the group consisting of a polydimethylsiloxane (PDMS), a polybenzoxazole, a polymer with intrinsic microporosity, or a mixture thereof;
wherein the microporous inorganic UZM-5 zeolite membrane comprises at least 95% UZM-5 zeolites.

### Claim 6 (depends on 5)

The method of claim 5 further comprising contacting the inorganic UZM-5 membrane obtained in step (i) with the said aged UZM-5 zeolite-forming gel again and repeating steps (h) to (i) at least one time.

### Claim 7 (depends on 5)

The method of claim 5 wherein said UZM-5 zeolite seeds in the as synthesized form are synthesized by a hydrothermal synthesis method or a microwave assisted hydrothermal synthesis method.

### Claim 8 (depends on 5)

The method of claim 5 wherein said membrane is in a form selected from the group consisting of disk, tube and hollow fiber.

### Claim 9

A process for separating at least one gas from a mixture of gases comprising:
(a) providing a microporous inorganic UZM-5 zeolite membrane which is permeable to said at least one gas;
(b) contacting the mixture on one side of the microporous inorganic UZM-5 zeolite membrane to cause said at least one gas to permeate the microporous inorganic UZM-5 zeolite membrane; and
(c) removing from the opposite side of the membrane a permeate gas composition comprising a portion of said at least one gas;
wherein the microporous inorganic UZM-5 zeolite membrane comprise at least 95% UZM-5 zeolites.

### Claim 10 (depends on 9)

The process of claim 9 wherein said mixture of gases is selected from the group consisting of CO2/CH4, H2S/CH4, N2/CH4, CO2/H2, CO2/N2, H2/CH4, O2/N2, olefin/paraffin mixtures and iso/normal paraffins.

### Claim 11 (depends on 9)

The process of claim 9 wherein mixture of gases are mixtures of at least one gas selected from the group consisting of H2O, H2S, and NH3/mixtures with at least one gas selected from the group consisting of CH4, N2, and H2.

### Claim 12

A microporous inorganic UZM-5 zeolite membrane.

### Claim 13 (depends on 12)

The microporous inorganic UZM-5 zeolite membrane of claim 12 wherein said UZM-5 zeolite is nano-sized UZM-5 zeolite with particle size <1 μm.

### Claim 14 (depends on 12)

The microporous inorganic UZM-5 zeolite membrane of claim 12 wherein said UZM-5 zeolite is selected from the group consisting of UZM-5, UZM-5P and UZM-5HS.