Multilayer aromatic polyamide thin-film composite membranes for separation of gas mixtures

Patent metadata

Field	Value
Publication number	US-11724230-B2
Application number	US-202016870577-A
Country	US
Kind code	B2
Filing date	May 8, 2020
Priority date	Jul 7, 2017
Publication date	Aug 15, 2023
Grant date	Aug 15, 2023

Abstract

A gas separation membrane for selective separation of hydrogen and helium from gas mixtures containing carbon dioxide includes a porous support layer, an aromatic polyamide layer on the porous support layer, and a coating including a glassy polymer formed on the aromatic polyamide layer. A glass transition temperature of the glassy polymer is greater than 50° C. The gas separation membrane may be formed by contacting a solution including the glassy polymer with an aromatic polyamide layer of a composite membrane and drying the solution to form a coating of the glassy polymer on the aromatic polyamide layer. Separating hydrogen or helium from a gas stream including carbon dioxide includes contacting a gas feed stream including carbon dioxide with the gas separation membrane to yield a permeate stream having a concentration of helium or hydrogen that exceeds the concentration of helium or hydrogen, respectively, in the gas feed stream.

First claim

What is claimed is:

1. A gas separation membrane comprising:
a hollow fiber membrane comprising:
a porous support layer with a thickness between 30 μm and 100 μm;
an aromatic polyamide layer with a thickness between 20 nm and 200 μm formed on the porous support layer via interfacial polymerization; and
a coating with a thickness of less than 1 μm comprising a glassy polymer formed on the aromatic polyamide layer and that plugs defects in the aromatic polyamide layer, wherein a glass transition temperature of the glassy polymer is greater than 50° C., and wherein the hollow fiber membrane has a selectivity of helium over carbon dioxide greater than 40 after coating,
wherein the glassy polymer is poly(phenylene oxide).

2. The membrane of claim 1 , wherein the glassy polymer is functionalized.

3. The membrane of claim 1 , wherein the glassy polymer is sulfonated or halogenated.

4. The membrane of claim 1 , wherein the glassy polymer comprises a brominated poly(phenylene oxide).

5. The membrane of claim 1 , wherein the selectivity of helium over carbon dioxide is greater than 70 for the hollow fiber membrane.

6. The membrane of claim 1 , wherein the selectivity of helium over methane is greater than 70 for the hollow fiber membrane.

7. The membrane of claim 1 , wherein a helium permeance of the membrane is between 5 and 150 GPU (10-6 cm3(STP)/cm2/sec/cmHg) at an operating feed pressure of 50 psia.

8. A method of making a hollow fiber membrane for gas separation, the method comprising:
dissolving a glassy polymer in a solvent to yield a solution, wherein the glassy polymer has a glass transition temperature greater than 50° C.;
contacting the solution comprising the glassy polymer with an aromatic polyamide layer of a thickness between 20 nm and 200 μm, wherein the aromatic polyamide layer is formed by interfacial polymerization over a porous support of a thickness of between 30 μm and 100 μm layer; and
drying the solution to form a coating of the glassy polymer on the aromatic polyamide layer, wherein the coating has a thickness less than 1 μm, and wherein the hollow fiber membrane has selectivity of helium over carbon dioxide of greater than 40,
wherein the glassy polymer is poly(phenylene oxide).

9. The method of claim 8 , wherein the solvent comprises chloroform.

10. The method of claim 8 , wherein contacting the solution with the aromatic polyamide layer comprises slot die coating, spin coating, dip coating, or spray coating the solution on the aromatic polyamide layer.

11. A gas separation method comprising:
contacting a gas feed stream comprising carbon dioxide and at least one of helium and hydrogen with a gas separation membrane comprising a hollow fiber membrane to yield a permeate stream and a reject stream, wherein a concentration of helium or hydrogen in the permeate stream exceeds the concentration of helium or hydrogen, respectively, in the gas feed stream, wherein the gas separation membrane has a selectivity of helium over carbon dioxide greater than 40, and wherein the gas separation membrane comprises:
a porous support layer;
an aromatic polyamide layer with a thickness between 20 nm and 200 μm formed on the porous support layer via interfacial polymerization, wherein the porous support layer has a thickness of between 30 μm and 100 μm; and
a coating comprising a glassy polymer formed on the aromatic polyamide layer wherein the coating is less than 1 μm in thickness, wherein a glass transition temperature of the glassy polymer is greater than 50° C.,
wherein the glassy polymer is poly(phenylene oxide).

12. The method of claim 11 , wherein the gas feed stream comprises at least 100 ppm by volume of helium, hydrogen, or a combination thereof.

13. The method of claim 11 , wherein the gas feed stream comprises up to 90 vol % of helium, hydrogen, or a combination thereof.

14. The method of claim 11 , wherein the permeate stream comprises at least 90 vol % of the helium in the gas feed stream, at least 90 vol % of the hydrogen in the gas feed stream, or both.

15. The method of claim 11 , wherein the permeate stream comprises at least 85 vol % of helium, at least 85 vol % of hydrogen, or at least 85 vol % of a combination of helium and hydrogen.

16. The method of claim 11 , wherein:
the hollow fiber membrane is mounted in a hollow fiber membrane module;
the gas feed stream is provided to an outer surface of the hollow fiber membrane; and
flowing a sweep gas through the inside of the hollow fiber membrane to remove the permeate stream from the hollow fiber membrane.

Assignees

• Saudi Arabian Oil Co

Inventors

• Choi Seung-Hak
• Al-Qahtani Mohammad S
• Qasem Eyad A

Classifications

• B01D69/12

  Composite membranes; Ultra-thin membranes · CPC title

• B01D71/5223

  Polyphenylene oxide, phenyl ether polymers or polyphenylethers · CPC title

• B01D71/5222

  Polyetherketone, polyetheretherketone, or polyaryletherketone · CPC title

• B01D69/1251

  by interfacial polymerisation · CPC title

• B01D71/64

  Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors · CPC title