Graphene-Ceramic Composite Membrane for Hydrogen Separation Membranes

Patent metadata

Field	Value
Publication number	US-2019119110-A1
Application number	US-201816158366-A
Country	US
Kind code	A1
Filing date	Oct 12, 2018
Priority date	Oct 20, 2017
Publication date	Apr 25, 2019
Grant date	—

Abstract

A hydrogen permeation membrane is provided that can include a carbon-based material (C) and a ceramic material (BZCYT) mixed together. The carbon-based material can include graphene, graphite, carbon nanotubes, or a combination thereof. The ceramic material can have the formula BaZr 1-x-y-z Ce x Y y T z O 3-δ , where 0≤x≤0.5, 0≤y≤0.5, 0≤z≤0.5, (x+y+z)>0; 0≤δ≤0.5, and T is Yb, Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, or a combination thereof. In addition, the BZYCT can be present in the C-BZCYT mixture in an amount ranging from about 40% by volume to about 80% by volume. Further, a method of forming such a membrane is also provided. A method is also provided for extracting hydrogen from a feed stream.

First claim

What is claimed:

1 . A hydrogen permeation membrane, comprising: a carbon-based material and a ceramic material mixed together, wherein the carbon-based material comprises graphene, graphite, carbon nanotubes, or a combination thereof, and wherein the ceramic material has the formula:
BaZr 1-x-y-z Ce x Y y T z O 3-δ where 0≤x≤0.5, 0≤y≤0.5, 0≤z≤0.5, (x+y+z)>0, 0≤δ≤0.5, and T is Yb, Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, or a combination thereof.

2 . The hydrogen permeation membrane of claim 1 , comprising the ceramic material in about 40% to about 80% by volume.

3 . The hydrogen permeation membrane of claim 1 , wherein the hydrogen permeation membrane has a thickness of about 0.01 mm to about 10 mm.

4 . The hydrogen permeation membrane of claim 1 , where 0<x≤0.5, 0<y≤0.5, and 0<z≤0.5.

5 . The hydrogen permeation membrane of claim 4 , wherein the carbon-based material is graphene.

6 . The hydrogen permeation membrane of claim 4 , where 0<δ≤0.5.

7 . A method of forming a membrane, comprising:
mixing a carbon-based material and a ceramic powder to form a carbon-ceramic mixture, wherein the carbon based material comprises graphene, graphite, carbon nanotubes, or a combination thereof; pressing the carbon-ceramic mixture to form a composite membrane; and sintering the carbon-ceramic mixture at a temperature of about 1100° C. to about 1700° C., wherein the ceramic powder comprises a ceramic material having the formula:
BaZr 1-x-y-z Ce x Y y T z O 3-δ
where 0≤x≤0.5, 0≤y≤0.5, 0≤z≤0.5, (x+y+z)>0; 0≤δ≤0.5, and T is Yb, Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, or a combination thereof.

8 . The method of claim 7 , wherein the carbon-ceramic mixture is sintered in a reducing atmosphere.

9 . The method of claim 8 , wherein the reducing atmosphere comprises H 2 .

10 . The method of claim 7 , further comprising:
heating the carbon-ceramic mixture is in an inert atmosphere prior to sintering in the reducing atmosphere.

11 . The method of claim 10 , wherein the inert atmosphere comprises N 2 .

12 . The method of claim 10 , wherein the inert atmosphere comprises Ar.

13 . The method of claim 7 , wherein the carbon-based material is graphene.

14 . The method of claim 7 , where 0≤x≤0.5, 0≤y≤0.5, and 0≤z≤0.5.

15 . The method of claim 14 , where 0≤δ≤0.5.

16 . The method of claim 7 , wherein the carbon-based material and the ceramic powder are mixed such that the carbon-ceramic mixture comprises the ceramic material in amount ranging from about 40% by volume to about 80% by volume.

17 . A method of extracting hydrogen from a feed stream, comprising:
exposing the feed stream to a first side of a membrane at a temperature of about 600° C. to about 1000° C., wherein the feed stream comprises hydrogen; and collecting pure hydrogen gas from a second side of the membrane opposite of the first side, wherein the membrane comprises a carbon-based material and a ceramic material, wherein the carbon-based material includes graphene, graphite, carbon nanotubes, or a combination thereof, and wherein the ceramic material has the formula:
BaZr 1-x-y-z Ce x Y y T z O 3-δ

where 0≤x≤0.5, 0≤y≤0.5, 0≤z≤0.5, (x+y+z)>0; 0≤δ≤0.5, and T is Yb, Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, or a combination thereof.

Assignees

• Univ South Carolina
• Univ Clemson

Inventors

• Chen Fanglin
• Fang Shumin
• Brinkman Kyle
• Wang Siwei
• He Jian
• Liu Yufei

Classifications

• C01F17/30

  Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 (C01F17/247 - C01F17/294 take precedence) · CPC title

• C04B2235/3256

  Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate · CPC title

• C04B2235/3232

  Titanium oxides or titanates, e.g. rutile or anatase · CPC title

• C04B2235/786

  Micrometer sized grains, i.e. from 1 to 100 micron · CPC title

• B01D2256/16

  Hydrogen · CPC title