Chemically stable ceramic-metal composite membrane for hydrogen separation
A hydrogen permeation membrane is provided that can include a metal and a ceramic material mixed together. The metal can be Ni, Zr, Nb, Ta, Y, Pd, Fe, Cr, Co, V, or combinations thereof, and the ceramic material can have the formula: BaZr 1-x-y Y x T y O 3-δ where 0≦x≦0.5, 0≦y≦0.5, (x+y)>0; 0≦δ≦0.5, and T is Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Sn, or combinations thereof. A method of forming such a membrane is also provided. A method is also provided for extracting hydrogen from a feed stream.
1. A hydrogen permeation membrane, comprising: a metal and a ceramic material mixed together, wherein the metal comprises Ni, and wherein the ceramic material has the formula:
BaZr 1-x-y Y x T y O 3-δ
where
0<x≦0.5,
0≦y≦0.5,
0<(x+y)<1;
0≦δ≦0.5, and
T is Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Sn, or combinations thereof, wherein at least a portion of the ceramic material is prepared with EDTA, citric acid, or a combination thereof prior to mixing with the metal.
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<y≦0.5.
5. The hydrogen permeation membrane of claim 4 , where 0<δ≦0.5.
6. A method of forming a membrane, comprising:
mixing a metal and a ceramic powder to form a metal-ceramic mixture, wherein the metal comprises Ni;
pressing the metal-ceramic mixture to form a composite membrane; and
sintering the metal-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 Y x T y O 3-δ
where 0<x≦0.5, 0≦y≦0.5, 0<(x+y)<1; 0≦δ≦0.5, and T is Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Sn, or combinations thereof, wherein at least a portion of the ceramic powder is prepared with EDTA, citric acid, or a combination thereof.
7. The method of claim 6 , wherein the metal-ceramic mixture is sintered in a reducing atmosphere.
8. The method of claim 7 , wherein the reducing atmosphere comprises H 2 .
9. The method of claim 6 , further comprising:
heating the metal-ceramic mixture is in an inert atmosphere prior to sintering in the reducing atmosphere.
10. The method of claim 9 , wherein the inert atmosphere comprises N 2 .
11. The method of claim 9 , wherein the inert atmosphere comprises Ar.
12. The method of claim 6 , where 0<y≦0.5.
13. The method of claim 12 , where 0<δ≦0.5.
14. The method of claim 6 , wherein the metal and the ceramic powder are mixed such that the metal-ceramic mixture comprises the ceramic material in about 40% to about 80% by volume.
15. 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 metal and a ceramic material, wherein the metal comprises Ni, and wherein the ceramic material has the formula:
BaZr 1-x-y Y x T y O 3-δ
where 0<x≦0.5, 0≦y≦0.5, 0<(x+y)<1; 0≦δ≦0.5, and T is Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Sn, or combinations thereof, wherein at least a portion of the ceramic material is prepared with EDTA, citric acid, or a combination thereof prior to mixing with the metal.
16. The hydrogen permeation membrane of claim 1 , wherein the grain size of the ceramic material is less than or equal to 1.17 μm.
17. The hydrogen permeation membrane of claim 1 , wherein a portion of the ceramic material is not sinter-active.
18. The hydrogen permeation membrane of claim 1 , wherein the ceramic material comprises BaZr 0.8 Y 0.2 O 3-δ .