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

• US 9,770,688 B2
• Filed: 10/22/2015
• Issued: 09/26/2017
• Est. Priority Date: 10/22/2015
• Status: Expired due to Fees

• Current Assignee: King Fahd University Of Petroleum And Minerals
• Original Assignee: King Fahd University Of Petroleum And Minerals
• Inventors: Zahir, Md. Hasan
• Primary Examiner(s): SHUMATE, ANTHONY R
• Application Number:
  US14/920,483
• Publication Number:
  US 20170113179A1
• Time in Patent Office: 705 Days
• CPC Class Codes: B01D 2053/221 Devices
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/18 Noble gases
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2323/48 Influencing the pH
• CPC Class Codes: B01D 2325/02831 less than 1 nm
• CPC Class Codes: B01D 2325/02832 1-10 nm
• CPC Class Codes: B01D 2325/04 Characteristic thickness
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0048 by sol-gel transition
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/10 Supported membranes; Membrane supports
• CPC Class Codes: B01D 69/108 Inorganic support material
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/027 : Silicium oxide
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

A nanocomposite membrane including an α-Al₂O₃ membrane support, a γ-Al₂O₃ intermediate layer that is 300-1200 nm thick and coats a surface of the membrane support, and a nanocomposite layer including SiO₂ and Y₂O₃ 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-Al₂O₃, 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.

Claims

1. A nanocomposite membrane, comprising:

a membrane support comprising tubular α

-Al₂O₃;

an intermediate layer comprising γ

-Al₂O₃, wherein the intermediate layer is 300-1200 nm thick and coats a surface of the membrane support;

a nanocomposite layer comprising SiO₂ and Y₂O₃, 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

-Al₂O₃ layers, each distinct γ

-Al₂O₃ layer being 150-600 nm thick.

3. The nanocomposite membrane of claim 1, wherein the Y₂O₃ is in the form of nanoparticles with a largest dimension of 1-6 nm, the nanocomposite layer is in the form of a SiO₂ matrix, and the Y₂O₃ nanoparticles are dispersed in or deposited onto the SiO₂ 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<sup>−

6</sup> mol/m²·

sec·

Pa for a first gas, and a membrane permeance of 1e<sup>−

10</sup>-1e<sup>−

9</sup> mol/m²·

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 H₂, He, or both, and the second gas is N₂, CO₂, or both.

8. The nanocomposite membrane of claim 1, which has a membrane permeance of 1e⁻

8-1e<sup>−

6</sup> mol/m²·

sec·

Pa for a first gas, and a membrane permeance of 1e<sup>−

10</sup>-1e<sup>−

9</sup> mol/m²·

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

-Al₂O₃ with the γ

-Al₂O₃ 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

-Al₂O₃ to form an intermediate layer comprising at least two distinct γ

-Al₂O₃ layers, each distinct γ

-Al₂O₃ 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<sup>−

6</sup> mol/m²·

sec·

Pa and the second gas has a permeance through the nanocomposite membrane of 1e<sup>−

10</sup>-1e<sup>−

9</sup> mol/m²·

sec·

Pa at 100-500°

C.

19. The method of claim 17, wherein the first gas is H₂, He, or both, and the second gas is N₂, CO₂, 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.