High temperature steam separation membrane

Patent metadata

Field	Value
Publication number	US-11617992-B2
Application number	US-202117168646-A
Country	US
Kind code	B2
Filing date	Feb 5, 2021
Priority date	Feb 5, 2021
Publication date	Apr 4, 2023
Grant date	Apr 4, 2023

Abstract

Ceramic proton-conducting oxide membranes are described herein, which are useful for separating steam from organic chemicals under process conditions. The membranes have a layered structure, with a dense film of the perovskite over a porous composite substrate comprising the perovskite material and a metallic material (e.g., Ni, Cu, or Pt). The perovskite comprises an ABO 3 -type structure, where “A” is Ba and “B” is a specified combination of Ce, Zr, and Y. The perovskite ceramic materials described herein have an empirical formula of Ba(Ce x Zr 1-x-n Y n )O 3-δ , wherein 0<x<0.8 (e.g., 0.1≤x≤0.7 or 0.2≤x≤0.5); and 0.05≤n≤0.2; and δ=n/2. In some embodiments n is about 0.2. In some other embodiments 0.6≤x≤0.8; and n is about 0.2, such as Ba(Ce 0.7 Zr 0.1 Y 0.2 )O 3-δ , also referred to herein as BCZY712.

First claim

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A porous membrane useful for steam separation, the membrane comprising:
(a) a shaped, porous substrate comprising a composite of a metal and a perovskite ceramic material of formula Ba(Ce x Zr 1-x-n Y n )O 3-δ , wherein 0<x<0.8; n is 0.2; and δ=n/2; and
(b) a dense film of the perovskite ceramic material of formula Ba(Ce x Zr 1-x-n Y n )O 3- δ contacting and covering a surface of the shaped, porous substrate.

2. The membrane of claim 1 , wherein 0.1≤x≤0.7.

3. The membrane of claim 1 , wherein 0.2≤x≤0.5.

4. The membrane of claim 1 , wherein 0.1≤x≤0.7.

5. The membrane of claim 1 , wherein 0.2≤x≤0.5.

6. The membrane of claim 1 , wherein the metal is selected from the group consisting of Ni, Cu, and Pt.

7. The membrane of claim 1 , wherein the porous substrate has a porosity of about 10 to about 40 volume percent.

8. The membrane of claim 1 , wherein the porous substrate has a porosity of about 30 volume percent.

9. The membrane of claim 1 , wherein the porous substrate has a thickness of about 0.5 to about 2 mm.

10. The membrane of claim 1 , wherein the dense film has a thickness of about 5 to about 30 μm.

11. The membrane of claim 1 , wherein the porous substrate has a thickness of about 0.5 to about 2 mm; and the dense film has a thickness of about 5 to about 30 μm.

12. The membrane of claim 1 , wherein the porous substrate comprises about 25 to about 100 percent by weight (wt %) of the perovskite and about 0 to about 75 wt % of the metal.

13. The membrane of claim 1 , wherein the porous substrate comprises about 40 wt % of the perovskite and about 60 wt % of the metal.

14. The membrane of claim 1 , wherein the membrane is in the shape of a tube and the dense film is on the interior of the tube.

15. A porous membrane useful for steam separation, the membrane comprising:
(a) a shaped, porous substrate comprising a composite of Ni and a perovskite ceramic material of formula Ba(Ce x Zr 1-x-n Y n )O 3-δ , wherein 0.6≤x≤0.8; n is 0.2; and δ=n/2; and
(b) a dense film of the perovskite ceramic material of formula Ba(Ce x Zr 1-x-n Y n )O 3-δ contacting and covering a surface of the shaped, porous substrate;
wherein the porous substrate has a thickness of about 0.5 to about 2 mm; the dense film has a thickness of about 5 to about 30 μm; the porous substrate has a porosity of about 10 to about 40 volume percent, and the porous substrate comprises about 25 to about 100 percent by weight (wt %) of the perovskite and about 0 to about 75 wt % of a metal selected from the group consisting of Ni, Cu, and Pt.

16. A porous membrane useful for steam separation, the membrane comprising:
(a) a shaped, porous substrate comprising a composite of Ni and a perovskite ceramic material of formula Ba(Ce x Zr 1-x-n Y n )O 3-δ , wherein x is about 0.7; n is about 0.2; and δ=n/2; and
(b) a dense film of the perovskite ceramic material of formula Ba(Ce x Zr 1-x-n Y n )O 3-δ contacting and covering a surface of the shaped, porous substrate;
wherein the porous substrate has a thickness of about 0.5 to about 2 mm; the dense film has a thickness of about 5 to about 30 μm; the porous substrate has a porosity of about 25 to about 35 volume percent; and the porous substrate comprises about 35 to about 45 wt % of the perovskite and about 55 to 65 wt % of a metal selected from the group consisting of Ni, Cu, and Pt.

17. The membrane of claim 16 , wherein the metal is Ni.

18. The membrane of claim 15 , wherein the metal is Ni.

19. The membrane of claim 15 , wherein the membrane is in the shape of a tube and the dense film is in the interior of the tube.

Assignees

• Uchicago Argonne Llc

Inventors

• Lee Tae H
• Balachandran Uthamalingam

Classifications

• B01D2325/02

  Details relating to pores or porosity of the membranes · CPC title

• B01D69/12

  Composite membranes; Ultra-thin membranes · CPC title

• B01D71/024 Primary

  Oxides · CPC title

• B01D63/063

  on the inner surface thereof · CPC title

• B01D2053/223

  with hollow tubes · CPC title