# US 11,999,621 B2 · Systems and methods for increasing the hydrogen permeance of hydrogen-separation membranes in situ

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- Number: US 11,999,621 B2
- Document ID: US11999621B2
- Status: Granted
- Kind: B2
- Application number: 18/169,795
- Filed: 2023-02-15
- Published: 2023-06-22
- Granted: 2024-06-04
- Earliest claimed: 2020-10-23
- Assignees: H2 PowerTech, LLC
- Applicants: H2 PowerTech, LLC
- Inventors: Charles R. Hill; Christopher J. Wright; William A. Pledger
- Web page: https://patentgrep.com/patent/US11999621B2

## CPC

- C01B 3/503: characterised by membranes
- B01D 53/22: by diffusion (manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00)
- B01D 65/02: Membrane cleaning or sterilisation {; Membrane regeneration}
- B01D 69/02: characterised by their properties
- B01D 71/02231: {Palladium}
- B01J 7/00: Apparatus for generating gases (production of inert gas mixtures B01J19/14; for generating specific gases, see the relevant subclasses, e.g. C01B, C10J {; in "air bags" on vehicles B60R21/26; for starter gas F02C7/26; blasting cartridges for producing gas under pressure F42B3/04})
- B01J 8/006: {by filtration}
- B01J 19/2475: {Membrane reactors}
- C01B 3/32: by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
- C01B 3/501: by diffusion
- B01D 2256/16: Hydrogen
- B01D 2257/502: Carbon monoxide
- B01D 2257/504: Carbon dioxide
- B01D 2321/18: Use of gases
- B01D 2325/06: Surface irregularities
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/041: In-situ membrane purification during hydrogen production
- C01B 2203/049: the impurity being carbon
- C01B 2203/066: with fuel cells
- C01B 2203/1076: Copper or zinc-based catalysts
- C01B 2203/1223: Methanol
- C01B 2203/143: Three or more reforming, decomposition or partial oxidation steps in series
- Y02C 20/40: of CO2
- Y02E 60/50: Fuel cells
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Hydrogen-producing fuel processing systems and related methods. The systems include a hydrogen-producing region configured to produce a mixed gas stream from a feedstock stream, a hydrogen-separation membrane module having at least one hydrogen-selective membrane and configured to separate the mixed gas stream into a product hydrogen stream and a byproduct stream, and an oxidant delivery system configured to deliver an oxidant-containing stream to the hydrogen-separation membrane module in situ to increase hydrogen permeance of the hydrogen-selective membrane. The methods include operating a hydrogen-producing fuel processing system in a hydrogen-producing regime, and subsequently operating the hydrogen-producing fuel processing system in a restoration regime, in which an oxidant-containing stream is delivered to the hydrogen-separation membrane module in situ to expose the at least one hydrogen-selective membrane to the oxidant-containing stream to increase the hydrogen permeance of the at least one hydrogen-selective membrane.

## Claims

### Claim 1

A hydrogen-producing fuel processing system, the system comprising:
a hydrogen-producing region configured to produce a mixed gas stream that includes hydrogen as a majority component;
a hydrogen-separation membrane module including at least one hydrogen-selective membrane and configured to receive at least a portion of the mixed gas stream and to separate the mixed gas stream into a product hydrogen stream and a byproduct stream;
a heating assembly configured to maintain the hydrogen-separation membrane module at a predetermined hydrogen-separation membrane module restoration temperature of at least 200° C.; and
an oxidant delivery system configured to selectively deliver an oxidant-containing stream to the hydrogen-separation membrane module in situ and selectively expose at least a portion of the at least one hydrogen-selective membrane to the oxidant-containing stream to increase a hydrogen permeance of the at least one hydrogen-selective membrane; and
wherein the hydrogen-producing fuel processing system is configured to operate in a restoration regime in which the heating assembly maintains the hydrogen separation membrane module at the predetermined hydrogen-separation membrane module restoration temperature and the oxidant delivery system delivers the oxidant-containing stream to the hydrogen-separation membrane module.

### Claim 2 (depends on 1)

The system of claim 1, wherein the at least one hydrogen-selective membrane separates the hydrogen-separation membrane module into a mixed gas region and a permeate region, wherein the mixed gas stream is received within the mixed gas region, wherein the at least one hydrogen-selective membrane is configured to permit hydrogen gas contained within the mixed gas stream to diffuse through the at least one hydrogen-selective membrane to the permeate region to separate the mixed gas stream into the product hydrogen stream and the byproduct stream, wherein the byproduct stream is a portion of the mixed gas stream that does not diffuse through the at least one hydrogen-selective membrane and the product hydrogen stream is a portion of the mixed gas stream that diffuses through the at least one hydrogen-selective membrane, and wherein the oxidant delivery system is configured to deliver the oxidant-containing stream to the mixed gas region of the hydrogen-separation membrane module.

### Claim 3 (depends on 2)

The system of claim 2, wherein the at least one hydrogen-selective membrane comprises a mixed gas face and an opposed permeate face, wherein the mixed gas face is positioned in the mixed gas region of the hydrogen-separation membrane module and the permeate face is positioned in the permeate region of the hydrogen-separation membrane module, and wherein the oxidant delivery system is configured to selectively expose the mixed gas face of the at least one hydrogen-selective membrane to the oxidant-containing stream.

### Claim 4 (depends on 1)

The system of claim 1, wherein the oxidant delivery system comprises one or more oxidant stream inlets through which the oxidant delivery system is configured to flow the oxidant-containing stream to the hydrogen-separation membrane module, wherein the one or more oxidant stream inlets includes an oxidant stream inlet that is positioned upstream of the hydrogen-producing region.

### Claim 5 (depends on 4)

The system of claim 4, wherein at least one of the one or more oxidant stream inlets is interconnected with a fuel inlet port of the hydrogen-producing region.

### Claim 6 (depends on 4)

The system of claim 4, wherein the hydrogen-producing region includes a reforming catalyst, and further wherein the reforming catalyst is non-pyrophoric.

### Claim 7 (depends on 1)

The system of claim 1, wherein the oxidant delivery system comprises one or more oxidant stream inlets through which the oxidant delivery system is configured to flow the oxidant-containing stream to the hydrogen-separation membrane module, wherein the one or more oxidant stream inlets includes an oxidant stream inlet that is positioned downstream of the hydrogen-producing region.

### Claim 8 (depends on 1)

The system of claim 1, wherein the oxidant delivery system is configured to deliver the oxidant-containing stream to the hydrogen-separation membrane module while the hydrogen-separation membrane module is operably installed within the hydrogen-producing fuel processing system.

### Claim 9 (depends on 1)

The system of claim 1, wherein the oxidant delivery system is configured to deliver the oxidant-containing stream to the hydrogen-separation membrane module for a predetermined duration of oxidant supply time, and wherein the predetermined duration of oxidant supply time is at least one of at least 60 minutes and at most 2,880 minutes.

### Claim 10 (depends on 1)

The system of claim 1, wherein the oxidant delivery system is configured to deliver the oxidant-containing stream with a predetermined oxidant-containing stream flow rate, and wherein the oxidant-containing stream flow rate is at least one of at least 0.0001 standard liters per minute and at most 3 standard liters per minute.

### Claim 11 (depends on 1)

The system of claim 1, wherein the oxidant-containing stream includes oxygen as an oxidant.

### Claim 12 (depends on 1)

The system of claim 1, wherein the hydrogen-producing fuel processing system is configured to operate in a hydrogen-producing regime and in the restoration regime, wherein the hydrogen-producing fuel processing system is configured to generate hydrogen in the hydrogen-producing regime, and wherein the hydrogen-producing fuel processing system is configured to increase hydrogen permeance of the hydrogen-separation membrane module in the restoration regime, and wherein the heating assembly is configured to maintain one or more components of the hydrogen-producing fuel processing system in one or more predetermined restoration temperatures when the hydrogen-producing fuel processing system is operated in the restoration regime.

### Claim 13 (depends on 12)

The system of claim 12, wherein the predetermined restoration temperature is at least 375° C. and at most 425° C.

### Claim 14 (depends on 1)

The system of claim 1, wherein the oxidant delivery system is configured to increase the hydrogen permeance of the at least one hydrogen-selective membrane by selectively removing permeance-decreasing contaminants from the at least one hydrogen-selective membrane.

### Claim 15 (depends on 14)

The system of claim 14, wherein the oxidant delivery system is configured to selectively oxidize the permeance-decreasing contaminants to remove the permeance-decreasing contaminants from the at least one hydrogen-selective membrane.

### Claim 16 (depends on 1)

The system of claim 1, wherein the oxidant delivery system is configured to increase the hydrogen permeance of the at least one hydrogen-selective membrane by selectively increasing a surface roughness of the at least one hydrogen-selective membrane.

### Claim 17 (depends on 1)

A method of increasing hydrogen permeance of a hydrogen-separation membrane module in situ within a hydrogen-producing fuel processing system, the method comprising:
operating the hydrogen-producing fuel processing system of claim 1 in a hydrogen-producing regime, the method comprising:
supplying, by a feedstock delivery system, a feedstock stream to the hydrogen-producing region;
producing, by the hydrogen-producing region, the mixed gas stream containing hydrogen gas as the majority component and delivering the mixed gas stream to the hydrogen-separation membrane module;
separating, by the hydrogen-separation membrane module, the mixed gas stream into the product hydrogen stream and the byproduct stream; and
operating the hydrogen-producing fuel processing system in a restoration regime, comprising:
delivering, by the oxidant delivery system, the oxidant-containing stream to the hydrogen-separation membrane module in situ; and
selectively exposing at least the portion of the least one hydrogen-selective membrane of the hydrogen-separation membrane module to the oxidant-containing stream.

### Claim 18 (depends on 17)

The method of claim 17, wherein the method further comprises maintaining the hydrogen-separation membrane module at a membrane restoration temperature of at least 200° C.

### Claim 19 (depends on 17)

The method of claim 17, further comprising:
detecting one or more operational parameters within the hydrogen-producing fuel processing system during the operating in the hydrogen-producing regime, and determining whether at least one operational parameter of the one or more the operational parameters has passed a respective predetermined threshold; and
transitioning the hydrogen-producing fuel processing system from the hydrogen-producing regime to the restoration regime when the determining comprises determining that an operational parameter of the one or more operational parameters has passed the respective predetermined threshold.

### Claim 20 (depends on 17)

The method of claim 17, wherein the determining comprises determining whether a hydrogen-producing region temperature of the hydrogen-producing region has passed a predetermined hydrogen-producing region threshold temperature, wherein the transitioning comprises transitioning the hydrogen-producing fuel processing system from the hydrogen-producing regime to the restoration regime when the hydrogen-producing region temperature has passed the predetermined hydrogen-producing region threshold temperature, and wherein the hydrogen-producing region threshold temperature is at least one of at least 550° C. and at most 650° C.

### Claim 21 (depends on 17)

The method of claim 17, wherein the determining comprises determining whether a hydrogen permeance of the hydrogen-separation membrane module is at least a preselected threshold fraction of a preselected target hydrogen permeance, and wherein the transitioning comprises transitioning the hydrogen-producing fuel processing system from the hydrogen-producing regime to the restoration regime when the hydrogen permeance of the hydrogen-separation membrane module is less than the preselected threshold fraction of the preselected target hydrogen permeance.

### Claim 22 (depends on 17)

The method of claim 17, wherein the operating the hydrogen-producing fuel processing system in the restoration regime comprises increasing hydrogen permeance of the at least one hydrogen-selective membrane.