Hydrogen Production with Membrane Reformer

Patent metadata

Field	Value
Publication number	US-2021395083-A1
Application number	US-202016905790-A
Country	US
Kind code	A1
Filing date	Jun 18, 2020
Priority date	Jun 18, 2020
Publication date	Dec 23, 2021
Grant date	—

Abstract

A system and method of producing hydrogen, including converting hydrocarbon to methane via steam and pre-reforming catalyst in a pre-reformer, converting the methane to hydrogen and carbon dioxide by steam reforming via a reforming catalyst in a membrane reformer, diffusing through hydrogen through a tubular membrane in the membrane reformer.

First claim

What is claimed is:

1 . A method of producing hydrogen, comprising:
feeding hydrocarbon and steam to a pre-reformer having a pre-reforming catalyst; converting hydrocarbon to methane via the pre-reforming catalyst in the pre-reformer to give a pre-reformed intermediate that is a methane-rich mixture; feeding the pre-reformed intermediate to a membrane reformer, wherein the membrane reformer comprises a vessel, a reforming catalyst disposed in the vessel, and a tubular membrane disposed in the vessel; converting methane in the pre-reformed intermediate to hydrogen and carbon dioxide by steam reforming via the reforming catalyst in the membrane reformer in a region in the vessel external to the tubular membrane, wherein the region is a retentate side of the tubular membrane; and diffusing the hydrogen from the region through the tubular membrane into a bore of the tubular membrane, wherein the tubular membrane is hydrogen selective, and wherein the bore is a permeate side of the tubular membrane.

2 . The method of claim 1 , wherein producing hydrogen comprises producing hydrogen in a range of 20 normal cubic meter per hour (Nm 3 /hr) to 10,000 Nm 3 /hr.

3 . The method of claim 1 , comprising converting hydrocarbon, in addition to the methane, in the pre-reformed intermediate in the membrane reformer to hydrogen and carbon dioxide, wherein the steam reforming occurs at less than 600° C. in the vessel, wherein the region comprises a reaction space for the steam reforming, and wherein diffusing the hydrogen through the tubular membrane is contemporaneous with converting the methane to the hydrogen.

4 . The method of claim 1 , comprising:
providing a sweep gas to the bore; displacing the hydrogen from the bore with the sweep gas; increasing driving force for hydrogen permeation through the tubular membrane to the bore from the region via displacing the hydrogen from the bore with the sweep gas; and discharging a hydrogen stream from the bore.

5 . The method of claim 4 , comprising condensing steam in the hydrogen stream and removing the steam as condensed from the hydrogen stream, wherein the sweep gas comprises steam, and wherein the hydrogen stream as discharged from the bore comprises at least 90 mole percent (mol %) hydrogen on a dry-basis.

6 . The method of claim 4 , comprising:
purifying the hydrogen stream to give hydrogen product comprising at least 99.9 mol % hydrogen; and compressing the hydrogen product to a pressure of at least 350 bar.

7 . The method of claim 6 , wherein the purifying comprises routing the hydrogen stream through a vessel having adsorbent and removing components from the hydrogen stream via the absorbent.

8 . The method of claim 6 , wherein the purifying and the compressing are performed via an electrochemical compressor.

9 . The method of claim 1 , comprising:
discharging a carbon-dioxide stream from the region, the carbon-dioxide stream comprising at least 90 mole percent (mol %) carbon dioxide. condensing water in the carbon dioxide stream; removing the water as condensed from the carbon dioxide stream; and cryogenically purifying the carbon dioxide stream to give liquid carbon-dioxide product comprising at least 99 mol % carbon dioxide.

10 . The method of claim 1 , comprising providing heat to the membrane reformer via an electrical heater, wherein an operating temperature of the membrane reformer is less than 650° C., and wherein the hydrocarbon fed to the pre-reformer comprises naphtha, kerosene, gasoline, diesel, liquefied petroleum gas (LPG), natural gas or, mixture of hydrocarbons (C1 to C5), or any combinations thereof.

11 . The method of claim 1 , comprising removing sulfur compounds from the hydrocarbon prior to feeding the hydrocarbon to the pre-reformer, wherein the hydrocarbon as fed to the pre-reformer comprises less than 0.1 parts per million (ppm) of sulfur compounds comprising sulfur (S).

12 . The method of claim 1 , wherein the pre-reformer comprises the pre-reforming catalyst in an inlet portion of the vessel, and wherein the pre-reformer and the membrane reformer are an integrated unit.

13 . The method of claim 1 , comprising converting the methane to hydrogen via dry reforming catalyst disposed in an exit portion of the membrane reformer.

14 . A system for hydrogen production, comprising:
a pre-reformer to receive hydrocarbon and convert the hydrocarbon to methane via a pre-reforming catalyst; and a membrane reformer to receive the methane from the pre-reformer, the membrane reformer comprising:
a reforming catalyst in a vessel to convert the methane by steam reforming into hydrogen and carbon dioxide; and
a tubular membrane in the vessel to diffuse the hydrogen through the tubular membrane to a bore of the tubular membrane, wherein the tubular membrane is hydrogen selective and the bore is a permeate side of the tubular membrane, and wherein the reforming catalyst is disposed external to the tubular membrane; and
the vessel comprising a region in the vessel and external to the tubular membrane for the steam reforming, wherein the region is a retentate side of the tubular membrane.

15 . The system of claim 14 , wherein the membrane reformer to receive the methane in a methane-rich mixture from the pre-reformer, and wherein the tubular membrane comprises palladium.

16 . The system of claim 14 , comprising a conduit to provide steam to the pre-reformer and an electrical heater to provide heat to the membrane reformer for the steam reforming, wherein the vessel comprises a cylindrical vessel.

17 . The system of claim 16 , wherein the tubular membrane shares a longitudinal axis with the vessel.

18 . The system of claim 16 , wherein the tubular membrane is disposed concentrically in the vessel.

19 . The system of claim 14 , wherein the membrane reformer comprises a dry reforming catalyst in an outlet portion of the vessel.

20 . The system of claim 14 , wherein the pre-reformer comprises the pre-reforming catalyst in an inlet portion of the vessel, and wherein the pre-reformer and membrane reformer are integrated.

21 . The system of claim 14 , wherein the hydrocarbon comprises naphtha, kerosene, gasoline, diesel, liquefied petroleum gas (LPG), or any combinations thereof, and wherein the reforming catalyst is not in contact with the tubular membrane.

22 . The system of claim 14 , comprising a conduit to provide nitrogen or steam as sweep gas to the bore, wherein the system comprises a hydrogen production capacity in a range of 20 normal cubic meter per hour (Nm 3 /hr) to 10,000 Nm 3 /hr.

23 . The system of claim 22 , comprising an inner tube concentrically in the bore to facilitate flow of a sweep gas in the bore to displace hydrogen from the bore.

24 . The system of claim 14 , comprising a hydrogen purification system to process permeate from the bore to give hydrogen product comprising at least 99.9 mol % hydrogen, the hydrogen purification system comprising a condenser heat exchanger, a vessel having adsorbent, or an electrochemical compressor, or any combinations thereof.

25 . The system of claim 24 , comprising a compressor to increase pressure of the hydrogen product to at least 350 bar, wherein the compressor comprises the electrochemical compressor, a mechanical compressor, an ionic compressor, or a metal hydride compressor, or any combinations thereof.

26 . The system of clai

Assignees

• Saudi Arabian Oil Co

Inventors

• Harale Aadesh
• Jamal Aqil
• Paglieri Stephen N
• Van Veen Henk
• Sebastiani Francesco
• Katikaneni Sai P

Classifications

• B01J19/2475

  Membrane reactors · CPC title

• C01B2203/1035

  Catalyst coated on equipment surfaces, e.g. reactor walls · CPC title

• C01B3/382 Primary

  Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation · CPC title

• B01J8/009

  Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane · CPC title

• C01B2203/041

  In-situ membrane purification during hydrogen production · CPC title