# US 11,999,619 B2 · Hydrogen production with membrane reactor > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,999,619 B2 - Document ID: US11999619B2 - Status: Granted - Kind: B2 - Application number: 16/905,802 - Filed: 2020-06-18 - Published: 2021-12-23 - Granted: 2024-06-04 - Earliest claimed: 2020-06-18 - Assignees: Saudi Arabian Oil Company - Applicants: Saudi Arabian Oil Company - Inventors: Stephen N. Paglieri; Aadesh Harale - Web page: https://patentgrep.com/patent/US11999619B2 ## CPC - C01B 3/384: with external heating of the catalyst - B01D 53/227: {in parallel connexion} - B01D 53/228: {characterised by specific membranes} - B01D 69/04: Tubular membranes - B01D 71/02231: {Palladium} - B01J 19/0013: {Controlling the temperature of the process} - B01J 19/2415: {Tubular reactors} - B01J 19/2475: {Membrane reactors} - C01B 3/38: using catalysts - C01B 3/505: Membranes containing palladium - 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 2053/223: {with hollow tubes} - B01D 2256/16: Hydrogen - B01J 2219/00135: Electric resistance heaters - 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 2203/0475: the impurity being carbon dioxide - C01B 2203/085: by electric heating - C01B 2203/1035: Catalyst coated on equipment surfaces, e.g. reactor walls - C01B 2203/1058: Nickel catalysts - C01B 2203/1235: Hydrocarbons - C01B 2203/1241: Natural gas or methane - 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 ## Abstract A system and method for producing hydrogen, including providing hydrocarbon and steam into a vessel to a region external to a tubular membrane in the vessel. The method includes steam reforming the hydrocarbon in the vessel via reforming catalyst to generate hydrogen and carbon dioxide. The method includes diffusing the hydrogen through the tubular membrane into a bore of the tubular membrane, wherein the tubular membrane is hydrogen selective. ## Claims ### Claim 1 A hydrogen production system comprising: a vessel comprising an inlet to receive hydrocarbon; a reforming catalyst to convert the hydrocarbon into a product gas comprising hydrogen and carbon dioxide, wherein the reforming catalyst is disposed on an inside surface of a wall of the vessel and disposed on multiple resistive heaters in the vessel and an inner wall of the vessel; the multiple resistive heaters to heat the reforming catalyst and the hydrocarbon; electrical heaters disposed on an outside surface of the wall of the vessel; multiple tubular membranes that are hydrogen selective and disposed in the vessel to separate the hydrogen from the product gas into a respective bore of the multiple tubular membrane, the multiple tubular membranes positioned in the vessel in multiple pairs of tubular membranes, with each pair of tubular membranes sharing a longitudinal axis that is aligned with a central axis of the vessel, with each tubular membrane of a pair of tubular membranes comprising a capped end and positioned such that the capped ends of the tubular membranes of the pair of tubular membranes are adjacent; and a conduit collection header receives the hydrogen from the bore of the tubular membrane. ### Claim 2 (depends on 1) The hydrogen production system of claim 1, wherein the multiple resistive heaters comprise electrical cartridge heaters. ### Claim 3 (depends on 1) The hydrogen production system of claim 1, wherein the electrical heaters comprise electrical band heaters. ### Claim 4 (depends on 1) The hydrogen production system of claim 1, comprising a catalytic membrane reactor comprising the vessel, the reforming catalyst, the multiple electrical heaters, and the tubular membrane, wherein the tubular membrane comprises palladium or a palladium alloy. ### Claim 5 (depends on 1) The hydrogen production system of claim 1, wherein the vessel comprises a reaction space for steam reforming of the hydrocarbon, wherein the reaction space is external to the tubular membrane and is on the retentate side of the tubular membrane, wherein the bore is a permeate side of the tubular membrane, and wherein the hydrogen to diffuse from the product gas through a wall of the tubular membrane to the bore. ### Claim 6 (depends on 1) The hydrogen production system of claim 1, comprising a conduit coupling the bore to the conduit collection header. ### Claim 7 (depends on 1) The hydrogen production system of claim 1, comprising a conduit to provide nitrogen or steam as sweep gas to the bore. ### Claim 8 (depends on 1) The hydrogen production system of claim 1, comprising an inner tube concentrically in the bore to facilitate flow of a sweep gas in the bore to displace hydrogen from the bore toward the conduit collection header. ### Claim 9 (depends on 1) The hydrogen production system of claim 1, comprising an inner tube concentrically in the bore to facilitate flow of a sweep gas to displace hydrogen in a direction countercurrent to flow of the hydrocarbon and steam into the vessel. ### Claim 10 A catalytic membrane reactor for hydrogen production, comprising: a vessel comprising an inlet to receive hydrocarbon; a reforming catalyst in the vessel to convert the hydrocarbon into a product gas comprising hydrogen and carbon dioxide; electrical heaters disposed on an outside surface of a wall of the vessel; multiple electrical resistive heaters to heat the reforming catalyst and to provide heat to fluid in the vessel, wherein each of the multiple resistive heaters have a longitudinal axis offset and parallel to a longitudinal axis of each of multiple cylindrical membranes; and the multiple cylindrical membranes are hydrogen selective to separate permeate comprising hydrogen from the product gas via the permeate diffusing through a wall of each cylindrical membrane to a bore of each cylindrical membrane, wherein the bore of each cylindrical membrane is coupled to a conduit collection header, and wherein the conduit collection header is configured to receive the permeate from each bore, wherein the multiple cylindrical membranes are positioned in the vessel in multiple pairs of cylindrical membranes, with each pair of cylindrical membranes sharing an axis that is aligned with a longitudinal axis of the vessel, with each cylindrical membrane of a pair of cylindrical membranes comprising a capped end and positioned such that the capped ends of the cylindrical membranes of the pair of cylindrical membranes are adjacent. ### Claim 11 (depends on 10) The catalytic membrane reactor of claim 10, wherein the multiple electrical resistive heaters comprise electrical cartridge heaters. ### Claim 12 (depends on 10) The catalytic membrane reactor of claim 10, wherein the reforming catalyst comprises nickel. ### Claim 13 (depends on 10) The catalytic membrane reactor of claim 10, wherein the multiple cylindrical membranes comprise palladium or a palladium alloy. ### Claim 14 (depends on 10) The catalytic membrane reactor of claim 10, comprising a region in the vessel that is a reaction space for steam reforming the hydrocarbon, wherein the region is external to the multiple cylindrical membranes, wherein the bore of each cylindrical membrane is a permeate side of the cylindrical membrane, and wherein the region external to the multiple cylindrical membranes is a retentate side of the multiple cylindrical membranes. ### Claim 15 (depends on 10) The catalytic membrane reactor of claim 10, comprising an inner tube concentrically in the bore of each cylindrical membrane to facilitate flow of sweep gas to displace the permeate from the bore. ### Claim 16 (depends on 10) The catalytic membrane reactor of claim 10, wherein the reforming catalyst is disposed on the multiple electrical resistive heaters in the vessel. ### Claim 17 (depends on 16) The catalytic membrane reactor of claim 16, wherein the reforming catalyst is disposed on an inside surface of a wall of the vessel. ### Claim 18 (depends on 17) The catalytic membrane reactor of claim 17, comprising electrical heaters disposed on an outside surface of the wall of the vessel to heat the reforming catalyst disposed on the inside surface of the wall of the vessel and to provide heat to fluid in the vessel. ### Claim 19 (depends on 17) The catalytic membrane reactor of claim 17, wherein the reforming catalyst does not contact the multiple cylindrical membranes. ### Claim 20 (depends on 19) The catalytic membrane reactor of claim 19, wherein the reforming catalyst is packed inside the vessel. ### Claim 21 (depends on 20) The catalytic membrane reactor of claim 20, wherein the reforming catalyst packed inside the vessel contacts the multiple cylindrical membranes. ### Claim 22 (depends on 20) The catalytic membrane reactor of claim 20, wherein the reforming catalyst packed inside the vessel comprise pelletized catalyst. ### Claim 23 A hydrogen production system comprising: a vessel comprising an inlet to receive hydrocarbon; a reforming catalyst to convert the hydrocarbon into a product gas comprising hydrogen and carbon dioxide, wherein the reforming catalyst is disposed on an inside surface of a wall of the vessel and disposed on multiple resistive heaters in the vessel and an inner wall of the vessel; the multiple resistive heaters to heat the reforming catalyst and the hydrocarbon; electrical heaters disposed on an outside surface of the wall of the vessel; multiple tubular membranes that are hydrogen selective and disposed in the vessel to separate the hydrogen from the product gas into a respective bore of the multiple tubular membrane; a conduit collection header configured to receive the hydrogen from the bore of the tubular membrane; and a conduit configured to provide nitrogen or steam as a sweep gas to the respective bore of the multiple tubular membrane, the conduit comprising an inner tube concentrically positioned in the bore to facilitate flow of the sweep gas in the bore to displace hydrogen from the bore toward the conduit collection header. ### Claim 24 (depends on 23) The hydrogen production system of claim 23, wherein the multiple resistive heaters comprise electrical cartridge heaters, and the electrical heaters comprise electrical band heaters. ### Claim 25 (depends on 23) The hydrogen production system of claim 23, comprising a catalytic membrane reactor comprising the vessel, the reforming catalyst, the multiple electrical heaters, and the tubular membrane, wherein the tubular membrane comprises palladium or a palladium alloy. ### Claim 26 (depends on 23) The hydrogen production system of claim 23, wherein the vessel comprises a reaction space for steam reforming of the hydrocarbon, wherein the reaction space is external to the tubular membrane and is on the retentate side of the tubular membrane, wherein the bore is a permeate side of the tubular membrane, and wherein the hydrogen to diffuse from the product gas through a wall of the tubular membrane to the bore. ### Claim 27 (depends on 23) The hydrogen production system of claim 23, wherein the displaced hydrogen is in a direction countercurrent to flow of the hydrocarbon and steam into the vessel. ### Claim 28 (depends on 26) The hydrogen production system of claim 26, wherein the displaced hydrogen is in a direction countercurrent to flow of the hydrocarbon and steam into the vessel. ### Claim 29 A catalytic membrane reactor for hydrogen production, comprising: a vessel comprising an inlet to receive hydrocarbon; a reforming catalyst in the vessel to convert the hydrocarbon into a product gas comprising hydrogen and carbon dioxide; electrical heaters disposed on an outside surface of a wall of the vessel; multiple electrical resistive heaters to heat the reforming catalyst and to provide heat to fluid in the vessel, wherein each of the multiple resistive heaters have a longitudinal axis offset and parallel to a longitudinal axis of each of multiple cylindrical membranes; the multiple cylindrical membranes are hydrogen selective to separate permeate comprising hydrogen from the product gas via the permeate diffusing through a wall of each cylindrical membrane to a bore of each cylindrical membrane, wherein the bore of each cylindrical membrane is coupled to a conduit collection header, and wherein the conduit collection header is configured to receive the permeate from each bore; and an inner tube concentrically positioned in the bore of each cylindrical membrane to facilitate flow of sweep gas to displace the permeate from the bore of each cylindrical membrane to the conduit collection header. ### Claim 30 (depends on 29) The catalytic membrane reactor of claim 29, wherein the multiple electrical resistive heaters comprise electrical cartridge heaters. ### Claim 31 (depends on 29) The catalytic membrane reactor of claim 29, wherein the reforming catalyst comprises nickel. ### Claim 32 (depends on 29) The catalytic membrane reactor of claim 29, wherein the multiple cylindrical membranes comprise palladium or a palladium alloy. ### Claim 33 (depends on 29) The catalytic membrane reactor of claim 29, comprising a region in the vessel that is a reaction space for steam reforming the hydrocarbon, wherein the region is external to the multiple cylindrical membranes, wherein the bore of each cylindrical membrane is a permeate side of the cylindrical membrane, and wherein the region external to the multiple cylindrical membranes is a retentate side of the multiple cylindrical membranes. ### Claim 34 (depends on 29) The catalytic membrane reactor of claim 29, wherein the reforming catalyst is disposed on at least one of the multiple electrical resistive heaters in the vessel or an inside surface of a wall of the vessel. ### Claim 35 (depends on 29) The catalytic membrane reactor of claim 29, comprising electrical heaters disposed on an outside surface of the wall of the vessel to heat the reforming catalyst disposed on the inside surface of the wall of the vessel and to provide heat to fluid in the vessel.