SEPARATION MEMBRANE, HYDROGEN SEPARATION MEMBRANE INCLUDING THE SEPARATION MEMBRANE, AND DEVICE INCLUDING THE HYDROGEN SEPARATION MEMBRANE

US 2013 243 660A1

drawing #0

Show all 18 drawings

A separation membrane including an alloy, the alloy including at least one Group 5 element, and at least one selected from Pt and Ir.

PatentSwarm provides a collaborative workspace to search, highlight, annotate, and monitor patent data.

Start free trial Sign in

Tip: Select text to highlight, annotate, search, or share the selection.

Claims

1. A separation membrane comprising an alloy, the alloy comprising:
at least one Group 5 element;
at least one selected from Ti, Zr, and Hf; and
at least one selected from Pt and Ir.

Show 19 dependent claims

21-40. (canceled)

Description

This application claims priority to Korean Patent Application No. 10-2012-0027722, filed on Mar. 19, 2012 and Korean Patent Application No. 10-2013-0028218, filed on Mar. 15, 2013, and all the benefits accruing therefrom under 35 U.S.C. §119, the contents of which in their entireties are herein incorporated by reference.

BACKGROUND

1. Field

A separation membrane, a hydrogen separation membrane including the separation membrane, and a hydrogen separation device including the hydrogen separation membrane are disclosed.

2. Description of the Related Art

Recently, hydrogen has been in the spotlight as a clean energy source. As a separation membrane for selectively separating hydrogen from hydrogen-containing gases, various metal/metal alloys, silica/zeolite ceramics, metal ceramic composites (cermet), carbon-based polymer separation membranes, and the like are known. Among them, representatively, a Pd-based alloy separation membrane is commercially used (See, for example, Ockwig, N. and Nenoff, T., Membranes for Hydrogen Separation, Chemical Reviews, 107, 4078-4110, 2007, the content of which in its entirety is herein incorporated by reference). However, in the case of a Pd-based alloy, Pd itself is a noble metal and is expensive, and hydrogen separation performance of the alloy is improved by only about 2 to 3 times. Representative Pd-based alloys include PdAg23, PdCu40, and the like (See, for example, Knapton, A. G., Palladium Alloys for Hydrogen Diffusion Membranes, Platinum Metals Rev., 21, 44-50, 1977, the content of which in its entirety is herein incorporated by reference).

Accordingly, there remains a need for a lower cost hydrogen separation membrane that provides excellent hydrogen permeability.

SUMMARY

An embodiment provides a separation membrane that may suppress hydrogen embrittlement fractures and has improved hydrogen permeability.

Another embodiment provides a hydrogen separation membrane including the separation membrane.

Still another embodiment provides a hydrogen separation device including the hydrogen separation membrane.

According to an embodiment, a separation membrane includes an alloy, the alloy including at least one Group 5 element, and at least one selected from Pt and Ir is provided.

The separation membrane may include a crystalline structure and have a body-centered-cubic (BCC) structure formed by the at least one Group 5 element, and the at least one selected from Pt and Ir.

The body-centered-cubic structure may have a lattice constant of about 3.2 to about 3.4 .

The separation membrane may include equal to or less than about 20 atom % of the at least one selected from Pt and Ir.

The separation membrane may further include at least one selected from Ti and Hf.

The separation membrane, which further include at least one selected from Ti, Zr, and Hf, may also include a crystalline structure and have a body-centered-cubic (BCC) structure formed by the at least one Group 5 element, the at least one selected from Pt and Ir, and the at least one selected from Ti, Zr, and Hf.

The body-centered-cubic structure may have a lattice constant of about 3.2 to about 3.4 .

The separation membrane may include equal to or less than about 70 atom % of the at least one selected from Ti and Hf.

The separation membrane may include a non-porous dense layer structure having porosity of about 1 volume % to 0 volume %, based on the total volume of the separation membrane.

The separation membrane may have a thickness of about 1 to about 1000 micrometers (μm).

In an embodiment, the at least one Group 5 element may be V, Nb, or Ta.

In an embodiment, the at least one Group 5 element may be V or Nb.

In an embodiment, the separation membrane may include a binary alloy selected from at least one of VPt, NbPt, VIr, and NbIr.

In an embodiment, the separation membrane may include a ternary alloy selected from at least one of VTiPt, NbTiPt, and NbTiIr.

The separation membrane may have an elongation rate of about 5 to about 25%, when measured by ASTM E8M standard micro-tensile test.

The separation membrane may have a maximum load of about 200 to about 600 MPa, when measured by ASTM E8M standard micro-tensile test.

According to another embodiment, a hydrogen separation membrane including the separation membrane is provided.

The hydrogen separation membrane may have hydrogen solubility (a mole ratio of H/M, wherein H denotes hydrogen atoms and M denotes metal atoms of the alloy) of about 0.05 to about 0.25, when measured at 0.1 to 1 MPa hydrogen pressure and at 300° C. to 500° C.

The hydrogen separation membrane may have hydrogen solubility (a mole ratio of H/M, wherein H denotes hydrogen atoms and M denotes metal atoms of the alloy) of about 0.1 to about 0.2, when measured at 0.7 to 1 MPa hydrogen pressure and at 400° C.

The hydrogen separation membrane may have hydrogen permeability of about 1.0×108 to about 8.5×108 mol/m*s*Pa1/2 at 300° C. to 500° C.

The hydrogen separation membrane may further include a catalyst layer disposed on a side of the separation membrane.

The catalyst layer may include an alloy that includes at least one selected from Pd, Pt, Ru, and Ir, and at least one selected from Cu, Ag, Au, and Rh.

According to another embodiment, provided is a hydrogen separation device including: the hydrogen separation membrane disclosed above; an inlet chamber including an inlet for receiving a mixed gas including hydrogen gas; and a discharge chamber including an outlet for discharging a separated hydrogen gas, wherein the hydrogen separation membrane is disposed between the inlet chamber and the discharge chamber.

According to an embodiment, the hydrogen separation membrane may have a tubular shape, a cylindrical chamber barrier rib having a diameter which is greater than a diameter of the tubular hydrogen separation membrane may be disposed outside of the hydrogen separation membrane, the chamber barrier rib and the hydrogen separation membrane may define the inlet chamber, and an inner surface of the tubular hydrogen separation membrane may define the discharge chamber.

Also disclosed is a method of preparing the separation membrane disclosed above, the method including: heating at least one Group 5 element, at least one selected from Ti and Hf, and at least one selected from Pt and Ir to form an alloy; and forming a membrane from the alloy to form the separation membrane.

Also disclosed is a method of separating hydrogen, the method including: providing the hydrogen separation device disclosed above; providing a hydrogen containing gas at the inlet of the hydrogen separation device; and diffusing hydrogen through the hydrogen separation membrane of the hydrogen separation device to separate hydrogen.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other aspects, advantages and features of this disclosure will become more apparent by describing in further detail exemplary embodiments thereof with reference to the accompanying drawings, in which:

FIG. 1 schematically shows an embodiment of a crystal lattice structure of an alloy of the separation membrane;

FIG. 2 schematically shows an embodiment of a mechanism in which hydrogen gas effectively passes through a hydrogen separation membrane and is separated from other gases;

FIG. 3 is a schematic view showing an embodiment of a hydrogen separation device;

FIG. 4 is a schematic view showing another embodiment of a hydrogen separation device;

FIG. 5A is a graph of intensity (arbitrary units) versus scattering angle (degrees two-theta, 20) and shows the results of XRD analysis of the hydrogen separation membranes manufactured in Examples 4 and 5 and Comparative Example 1;

FIG. 5B is a graph of intensity (arbitrary units) versus scattering angle (degrees two-theta, 2θ) and is an expanded view of the portion of FIG. 5A between 37 and 41 degrees 2θ;

FIG. 6 is a graph of intensity (arbitrary units) versus scattering angle (degrees two-theta, 2θ) and shows the results of XRD analysis of the hydrogen separation membrane manufactured in Examples 7-9 and Comparative Example 1;

FIG. 7 is a graph of intensity (arbitrary units) versus scattering angle (degrees two-theta, 2θ) and shows the results of XRD analysis of the hydrogen separation membrane manufactured in Examples 12, 14, and 16, and Comparative Example 2;

FIG. 8 is a graph of intensity (arbitrary units) versus scattering angle (degrees two-theta, 2θ) and shows the results of XRD analysis of the hydrogen separation membrane manufactured in Examples 6 and 8 and Comparative Example 1;

FIG. 9 is a graph of stress (megaPascals, MPa) versus strain (percent, %) for the hydrogen separation membrane manufactured in Comparative Example 1;

FIG. 10 is a graph of stress (megaPascals, MPa) versus strain (percent, %) for the hydrogen separation membrane manufactured in Example 6;

FIG. 11 is a graph of stress (megaPascals, MPa) versus strain (percent, %) for the hydrogen separation membrane manufactured in Example 7;

FIG. 12 is a graph of stress (megaPascals, MPa) versus strain (percent, %) for the hydrogen separation membrane manufactured in Example 8;

FIG. 13 is a graph of stress (megaPascals, MPa) versus strain (percent, %) for the hydrogen separation membrane manufactured in Example 14;

FIG. 14 is graph of pressure (megaPascals, MPa) versus hydrogen content (hydrogen to metal ratio, H/M) and is a pressure-concentration-temperature (PCT) graph of the hydrogen separation membranes manufactured in Examples 1 and 10, and Comparative Examples 1, and 9;

FIG. 15 is graph of pressure (megaPascals, MPa) versus hydrogen content (hydrogen to metal ratio, H/M) and is a pressure-concentration-temperature (PCT) graph of the hydrogen separation membranes manufactured in Example 14, and Comparative Examples 3 to 7; and

FIG. 16 is graph of pressure (megaPascals, MPa) versus hydrogen content (hydrogen to metal ratio, H/M) and is a pressure-concentration-temperature (PCT) graph of the hydrogen separation membranes manufactured in Examples 13 and 15, and Comparative Examples 1, and 2.

DETAILED DESCRIPTION

The disclosed embodiments will be described more fully hereinafter in the following detailed description, in which some but not all embodiments of this disclosure are described. This disclosure may be embodied in many different forms and is not to be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout.

It will be understood that when an element is referred to as being on another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being directly on another element, there are no intervening elements present.

It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings herein.

PatentSwarm provides a collaborative workspace to search, highlight, annotate, and monitor patent data.

Start free trial Sign in