Si—Y nanocomposite membrane and methods of making and use thereof

Patent metadata

Field	Value
Publication number	US-9770688-B2
Application number	US-201514920483-A
Country	US
Kind code	B2
Filing date	Oct 22, 2015
Priority date	Oct 22, 2015
Publication date	Sep 26, 2017
Grant date	Sep 26, 2017

Abstract

A nanocomposite membrane including an α-Al 2 O 3 membrane support, a γ-Al 2 O 3 intermediate layer that is 300-1200 nm thick and coats a surface of the membrane support, and a nanocomposite layer including SiO 2 and Y 2 O 3 that is 25-150 nm thick and coats a surface of the intermediate layer, wherein the nanocomposite layer is porous with an average largest radius micropore of 0.2-0.6 nm. A method of manufacturing the nanocomposite membrane, whereby the membrane support is coated with the γ-Al 2 O 3 , a silica source is hydrolyzed with a mixture of water, an alcohol solvent, and a Y source with a sol-gel technique to yield a Si/Y sol-gel, the membrane support is dip coated with the Si/Y sol-gel, and the nanocomposite membrane is calcined. A method of separating a mixture of gas, whereby the mixture of gas is introduced into a permeance cell and fed through the nanocomposite membrane.

First claim

The invention claimed is:

1. A nanocomposite membrane, comprising:
a membrane support comprising tubular α-Al 2 O 3 ;
an intermediate layer comprising γ-Al 2 O 3 , wherein the intermediate layer is 300-1200 nm thick and coats a surface of the membrane support;
a nanocomposite layer comprising SiO 2 and Y 2 O 3 , wherein the nanocomposite layer is 25-150 nm thick and coats a surface of the intermediate layer;
wherein the nanocomposite layer is porous with an average largest radius micropore of 0.2-0.6 nm.

2. The nanocomposite membrane of claim 1 , wherein the intermediate layer comprises at least two distinct γ-Al 2 O 3 layers, each distinct γ-Al 2 O 3 layer being 150-600 nm thick.

3. The nanocomposite membrane of claim 1 , wherein the Y 2 O 3 is in the form of nanoparticles with a largest dimension of 1-6 nm, the nanocomposite layer is in the form of a SiO 2 matrix, and the Y 2 O 3 nanoparticles are dispersed in or deposited onto the SiO 2 matrix.

4. The nanocomposite membrane of claim 3 , wherein the nanocomposite layer is porous with an average mesopore radius of 1-4 nm.

5. The nanocomposite membrane of claim 1 , wherein the molar ratio of Si:Y in the nanocomposite membrane is 1:1 to 5:1.

6. The nanocomposite membrane of claim 1 , which has a membrane permeance of 1e −8 -1e −6 mol/m 2 ·sec·Pa for a first gas, and a membrane permeance of 1e −10 -1e −9 mol/m 2 ·sec·Pa for a second gas when a mixture of gas comprising the first gas and the second gas is fed through the nanocomposite membrane at a temperature of 100-650° C.

7. The nanocomposite membrane of claim 6 , wherein the first gas is H 2 , He, or both, and the second gas is N 2 , CO 2 , or both.

8. The nanocomposite membrane of claim 1 , which has a membrane permeance of 1e −8 -1e −6 mol/m 2 ·sec·Pa for a first gas, and a membrane permeance of 1e −10 -1e −9 mol/m 2 ·sec·Pa for a second gas when a mixture of gas comprising the first gas, the second gas, and up to 5 wt % of steam relative to the total weight of the mixture of gas is fed through the nanocomposite membrane.

9. The nanocomposite membrane of claim 8 , which has a permselectivity ranging from 60-400, wherein the permselectivity is calculated as the permeance of the first gas divided the permeance of the second gas.

10. A method of manufacturing the nanocomposite membrane of claim 1 , comprising
coating the membrane support comprising tubular α-Al 2 O 3 with the γ-Al 2 O 3 to form a membrane support coated with the intermediate layer,
hydrolyzing a silica source with a mixture comprising water, an alcohol solvent, and a Y source with a sol-gel technique to yield a Si/Y sol-gel,
dip coating the membrane support coated with the intermediate layer with the Si/Y sol-gel by a dip coating method, and
calcining in the presence of oxygen at 500-700° C.

11. The method of claim 10 , wherein the membrane support is coated at least two times with the γ-Al 2 O 3 to form an intermediate layer comprising at least two distinct γ-Al 2 O 3 layers, each distinct γ-Al 2 O 3 layer being 150-600 nm thick.

12. The method of claim 10 , further comprising repeating the dip coating and the calcining.

13. The method of claim 10 , wherein the molar ratio of the silica source to the Y source is 1:1 to 5:1.

14. The method of claim 10 , wherein the silica source is tetraethyl orthosilicate and the Y source is Yttrium(III) nitrate or hydrates thereof.

15. The method of claim 10 , further comprising adjusting the pH of the mixture to 0.5-4 by adding a mineral acid during the hydrolyzing.

16. The method of claim 10 , wherein the calcining is followed by cooling at a cooling rate of 0.1° C./min to 1.5° C./min to form the nanocomposite membrane.

17. A method of separating a mixture of gas comprising a first gas and a second gas, comprising:
introducing the mixture of gas into a gas feed side of a permeance cell comprising the gas feed side, a permeate side that opposes the gas feed side, and the nanocomposite membrane of claim 1 , wherein the nanocomposite layer of the nanocomposite membrane faces toward the gas feed side and forms a permeable barrier between the gas feed side and permeate side;
applying a vacuum to the permeate side; and
separating the first gas from the second gas by allowing the first gas to pass through the nanocomposite membrane and collect in the permeate side, and prohibiting the second gas from passing through the nanocomposite membrane and collect in the gas feed side.

18. The method of claim 17 , wherein the first gas has a permeance through the nanocomposite membrane of 1e −8 -1e −6 mol/m 2 ·sec·Pa and the second gas has a permeance through the nanocomposite membrane of 1e −10 -1e −9 mol/m 2 ·sec·Pa at 100-500° C.

19. The method of claim 17 , wherein the first gas is H 2 , He, or both, and the second gas is N 2 , CO 2 , or both.

20. The method of claim 17 , wherein a partial pressure of the mixture of gas introduced into the gas feed side is 110-200 kPa.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Zahir Md Hasan

Classifications

• B01D69/12

  Composite membranes; Ultra-thin membranes · CPC title

• B01D2053/221

  Devices · CPC title

• B01D69/10

  Supported membranes; Membrane supports · CPC title

• B01D71/024

  Oxides · CPC title

• B01D53/228 Primary

  characterised by specific membranes · CPC title