WO1999025649A1 - Hydrogen generator - Google Patents

Hydrogen generator Download PDF

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Publication number
WO1999025649A1
WO1999025649A1 PCT/GB1998/003410 GB9803410W WO9925649A1 WO 1999025649 A1 WO1999025649 A1 WO 1999025649A1 GB 9803410 W GB9803410 W GB 9803410W WO 9925649 A1 WO9925649 A1 WO 9925649A1
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Prior art keywords
catalyst
hydrogen
reactor according
catalyst bed
diffusion membrane
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PCT/GB1998/003410
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French (fr)
Inventor
Neil Edwards
Arjan Nicolaas Johan Van Keulen
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Johnson Matthey Public Limited Company
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Priority to GBGB9724203.6A priority Critical patent/GB9724203D0/en
Priority to GB9724203.6 priority
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO1999025649A1 publication Critical patent/WO1999025649A1/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631Reactor construction specially adapted for combination reactor/fuel cell
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382Multi-step processes
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405Purification by membrane separation
    • C01B2203/041In-situ membrane purification during hydrogen production
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435Catalytic purification
    • C01B2203/0445Selective methanation
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • C01B2203/1011Packed bed of catalytic structures, e.g. particles, packing elements
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • C01B2203/1023Catalysts in the form of a monolith or honeycomb
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1076Copper or zinc-based catalysts
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1082Composition of support materials
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217Alcohols
    • C01B2203/1223Methanol
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/146At least two purification steps in series
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Abstract

An autothermal reactor for producing high purity hydrogen from an organic feedstock, a source of oxygen and optionally water comprises a catalyst bed (13) for converting the feedstock into a hydrogen containing gas stream in association with a hydrogen diffusion membrane (9) which selectively separates hydrogen from the components of the gas stream. The hydrogen diffusion membrane preferably is in the form of a palladium based coil or spiral tube or a bundle of thin straight tubes or a palladium alloy supported on a porous ceramic substrate. The catalyst bed may be in the form of a granular bed of catalyst particles, a porous ceramic support material coated with catalyst, a porous ceramic foam coated with catalyst or a solid porous foam of catalyst. The catalyst bed and the hydrogen diffusion membrane preferably are located in the same reactor vessel and the catalyst bed is preferably positioned concentrically and coaxially around the hydrogen diffusion membrane.

Description

HYDROGEN GENERATOR

This invention relates to improvements in autothermal generators or reformers for the catalytic production of hydrogen from an organic fuel. More particularly, but not exclusively, this invention relates to improvements in self-igniting, self sustaining, autothermal catalytic hydrogen generators or reformers which can start up from ambient temperature.

The autothermal catalytic hydrogen generators or reformers to which this invention relates are of the type which can be operated by partial oxidation, steam reforming, water gas shift reaction or combinations thereof. Such reformers are disclosed in EP 0217532, EP 0262947 and WO 96/00186.

We have disclosed in EP 0217532, a self-igniting, self-sustaining, autothermal catalytic hydrogen generator or reformer the basic concept of which is that methanol and air are co-injected into the reactor containing an up-stream zone of a packed bed of a catalyst comprising copper on a refractory support with a down-stream zone containing a platinum or palladium catalyst mixed with a copper catalyst. The down-stream zone provides self- ignition to raise the reactor temperature to a point at which a hot spot is formed around the point of injection of feedstock into the upper bed of copper catalyst.

This hot spot concept was further developed in our invention disclosed in EP 0262947 which uses a reactor design which produces hydrogen from a hydrocarbon feedstock using a catalyst composed of platinum and chromium oxide on a support. Further details are given in a paper in Platinum Metals Review, 1989, 33 (3) 118-127.

In the course of scaling-up studies, we found, as described in WO 96/00186, that the output of the above mentioned reactors could be considerably increased by extending the injection/reaction zone interface whilst maintaining the short reaction time. This is achieved by replacing the single injector of the original hot spot reactors with a porous ceramic tube which acts as a multiple entry, high velocity, radial flow injection unit which causes a substantial pressure drop sufficient to prevent flow-back of feedstock or reaction products. The porous ceramic injection tube is surrounded by a shallow bed of catalyst so that the feedstock follows a radial path through the reactor. The catalyst is held in place by a copper gauze. A hot zone, as distinct from a hot spot, forms around the region where the feedstock enters the mass of the catalyst. It is believed that in the case of methanol feedstock, the hot zone is preferably at a temperature of 350 to 600°C. It was found that copper-based catalysts were very effective for self-sustaining hydrogen generation but it was necessary, however, to add a small amount of a precious metal catalyst to provide self-ignition and also to raise the catalyst bed temperature to a level at which the catalytic reaction becomes self- sustaining. Water, preferably, is co-fed with the feedstock as the presence of water gives various beneficial effects, as described in WO 96/00186.

Through an iterative process of reactor engineering, catalyst design and performance mapping, we have dramatically improved the performance of the above type of reactors, especially for methanol processing. The reactor contains a single bed of multicomponent noble metals/base metal catalyst. It produces hydrogen as soon as methanol/air or methanol/air/water enters the reactor and it can reach steady state within a minute. The reactor converts methanol very efficiently by a combination of partial oxidation (exothermic), steam-reforming (endothermic) and water gas shift reaction. By supplying a feed of methanol/water/air, the exothermic .and endothermic reactions can be made to sustain each other. Under these conditions, as much as 2.4 moles of hydrogen are produced for each mole of methanol consumed. Also, the maximum temperature inside the reactor is only 400°C excellent catalyst durability. As both the exothermic and endothermic reactions occur on the same catalyst particles, heat transfer occurs over very short (microscopic) distances as opposed to macro heat exchange. The hot spot or hot zone types of autothermal reactor described above can be designed to operate with a variety of organic feedstocks and catalysts and also different forms of catalyst bed.

Whilst the present invention is described mainly with reference to the above type of hot spot or hot zone types of autothermal reactor it is to be understood that it can be applied also to more conventional designs of autothermal fuel processors.

The reformate gas mixture produced by reforming organic fuels in self-igniting, self-sustaining, autothermal catalytic hydrogen generators, as described above, typically contains hydrogen, methane, carbon monoxide, carbon dioxide, oxygen and nitrogen. The concentration of carbon monoxide in the reformate gas depends on several factors, including the composition of the feedstock, and can be as high as 10vol%. Such concentrations are too high for the reformate gas to be used directly in many industrial and laboratory applications and steps have to be taken to lower the concentration of the carbon monoxide before use of the hydrogen-rich reformate.

The catalytic removal of carbon monoxide from a reformate gas mixture can be achieved by various techniques. These include (i) the selective oxidation of the carbon monoxide to carbon dioxide; (ii) the selective reduction of the carbon monoxide to methane; (iii) the reduction of the carbon monoxide with water vapour (water-gas shift) and (iv) the selective diffusion of hydrogen through a membrane which is more permeable to hydrogen than to carbon monoxide and other impurities of the reformate gas.

Several synthetic permeable membranes have been developed which can be used for selective separation and purification of hydrogen. These include noble metal membranes, ceramic membranes and zeolite membranes. One type of noble metal diffusion membrane comprises a thin palladium-based alloy tube (or tubes) in the form of a coil or spiral. Another type of noble metal membrane is in the form of a bundle of thin straight tubes. Yet another type of noble metal membrane consists of a thin layer of a palladium-based alloy supported on a porous ceramic substrate.

An objective of the present invention is to provide a self-igniting, self-sustaining, autothermal catalytic hydrogen generator which produces high purity hydrogen which can be used directly from the generator without further removal of carbon monoxide and other impurities. According to the present invention there is provided an autothermal reactor for producing high purity hydrogen from an organic feedstock, a source of oxygen and optionally water comprising a catalyst bed for converting the feedstock into a hydrogen containing gas stream in association with a hydrogen diffusion membrane which selectively separates hydrogen from the other components of the gas stream. Preferably, the catalyst bed and the hydrogen diffusion membrane are located in the same reactor vessel.

Further preferably, the hydrogen diffusion membrane is a palladium based membrane, a ceramic membrane or a zeolite membrane.

Suitably, the hydrogen diffusion membrane is a palladium based membrane in the form of a coil or spiral tube or in the form of a bundle of straight tubes. Alternatively, the hydrogen diffusion membrane comprises a thin film of palladium alloy supported on the upstream hydrogen contacting surface of a porous ceramic substrate.

A methanation catalyst may be deposited on the down stream surface of the porous ceramic substrate. The catalyst bed may take the form of granular bed of catalyst particles; a porous ceramic support material coated with the catalyst; a porous ceramic foam coated with the catalyst or the catalyst bed may take the form of a solid porous foam of the catalyst itself. Conveniently, the catalyst bed is positioned concentrically and co-axially around the hydrogen diffusion membrane. In one embodiment of the invention the catalyst bed is in the form of a granular bed of catalyst particles and the palladium based coiled or spiral tube or bundle of straight tubes is buried in the granular bed of catalyst particles.

In another embodiment of the invention the coiled or spiral tube may be wrapped around the catalytic bed. In the reactor of the invention, the heat generated by the catalytic reaction is used to help sustain the operating temperature of the hydrogen diffusion membrane. In some systems, however, the operating temperature of the catalytic bed may be higher than the operating temperature of the hydrogen diffusion membrane so there may be a need to recover some heat from the reformate. Conversely, higher temperature diffusers may be applicable, actually operating at a similar temperature to the catalyst bed. The reactor of the invention may operate by a combination of partial oxidation, steam reforming and water gas shift reaction.

Conveniently, the reactor of the invention is operated such that the temperature of the catalytic reaction is about the same or close to the optimum operating temperature of the hydrogen diffusion membrane. The reactor of the invention suitably may form part of a fuel cell system or a gas chromatography system.

The reactor of the invention preferably operates on similar principles to the reactors disclosed in WO 96/00186 in that multi-point radial entry of feedstock into a catalyst bed causes a significant pressure drop and results in high velocity injection of the feedstock into the catalyst bed. However, in most embodiments of the reactor of the invention, the feedstock enters from the outside of the catalyst bed and flows inwards through the bed, whereas the reverse arrangement is the case with the reactors described in WO 96/00186. An embodiment of the invention will now be described, simply by way of example, with reference to the accompanying drawing which is a schematic cross-section of a reactor according to the invention.

Referring to the drawing, the reactor housing consists of a stainless steel cylinder 1 , (height 12.5cm, diameter 5cm), closed at one end and with a stainless steel cover 2 fitted over the other end. The cover 2 is provided with inlet apertures 3 and 4 and an outlet aperture 5. The base of the cylinder 1 is provided with another outlet aperture 6. A flanged outlet tube 7 is fitted into outlet aperture 5 and another flanged outlet tube 8 is fitted into outlet aperture 6. A hydrogen diffusion membrane in the form of a palladium/silver alloy spiral tube 9 has one end 10 sitting on the flange 11 of outlet tube 8. The other end of spiral tube 9 is provided with a collar 12 which fits into the lower end of outlet tube 7. A solid permeable catalyst bed 13 is positioned concentrically and co-axially around spiral tube 9 and is retained between flange 11 of outlet tube 8 and flange 14 of outlet tube 7. The catalyst bed 13 may be located inside a porous ceramic multi-point feedstock injection tube (not shown) and may be held in position by a copper gauze (also not shown). Other designs of feedstock injection means may be utilised. A suitable catalyst bed composition is 5% Cu/Al2O3 and 5% Pd/Al2O3 mixed together in a ratio of 19:1 by mass. A feedstock consisting of a liquid mixture of methanol and water mixed with air is vaporised outside the reactor and introduced into the reactor by means of inlet apertures 3 and 4. The feedstock passes from the outside of the catalyst bed 13 into the body of the catalyst where it is catalytically converted by a combination of partial oxidation, steam reforming and water gas shift reaction into a hydrogen-rich gas stream containing approximately 50% hydrogen. It is the combination of these reactions which makes the reactor autothermal. The hydrogen-rich gas stream leaves the catalyst bed 13 and passes across palladium/silver alloy spiral tube 9. The hydrogen diffuses through spiral tube 9 producing a gas comprising at least 99.995% hydrogen at 45psig pressure which leaves the reactor by means of outlet tube 7. The gaseous impurities in the hydrogen-rich gas stream which did not diffuse through spiral tube 9 leave the reactor as a bleed stream through outlet tube 8. The bleed stream can be catalytically burned to remove bleed hydrogen, trace methanol and carbon monoxide. The heat from this after-burning can be used to heat the liquid entering the reactor or can be used somewhere else in the system.

The catalyst bed 13 operates at 8 to 10 bar pressure in order to generate enough pressure for the palladium/silver alloy spiral tube 9 to operate efficiently. This necessitates a compressor for the air and a liquid pump which can withstand these pressures. Furthermore, the hydrogen diffusion spiral tube 9 needs to operate at a minimum temperature of 300° C. The catalyst bed 13 may provide enough heat on its own to maintain the diffuser at its optimum operating temperature. The bleed stream of impurity gases which goes to vent through outlet tube 8 needs to be burned to remove any bleed hydrogen and methanol. The heat from this can be used to heat the feedstock liquids.

In another embodiment of the invention, the palladium/silver alloy diffusion tube 9 can be replaced by a bundle of straight palladium/silver alloy diffusion tubes.

In yet another embodiment of the invention, the palladium/silver alloy spiral diffusion tube 9 can be replaced by a hydrogen diffusion membrane in the form of a porous or microporous ceramic cylinder on the upstream surface of which is deposited a thin film of a palladium silver alloy. The downstream surface of the porous cylinder may have deposited on it a methanation catalyst which would serve to mop up any carbon monoxide which penetrates through the hydrogen diffusion membrane due to pin hole leaks in the membrane. The catalyst bed and the ceramic-supported membrane are concentric and co-axial. The ceramic-supported palladium based membrane requires a much lower pressure differential across the membrane than a membrane in the form of a spiral tube or a bundle of straight tubes. A 3 bar pressure drop across the ceramic-supported membrane is typical, (and other types of hydrogen diffusion membranes may require even lower pressures). Furthermore, the heat generated by the catalytic reaction maintains the membrane at its preferred temperature of operation.

In yet a further embodiment of the invention, a hydrogen diffusion membrane in the form of a coil or spiral tube or in the form of a bundle of thin tubes may be buried in a catalyst in the form of a granular catalytic bed.

Also, the coil or spiral tube or bundle of straight tubes can be positioned around the outside of the catalyst bed with in this case the gas flow being from inside to the outside of the bed. The autothermal reactor of the invention is particularly suitable for supply of pure hydrogen for small scale operations such as fuel cell systems for automotive purposes and for gas chromatography and other laboratory applications which require pure hydrogen. The present invention is particularly suitable for "portable" applications and does away with the need for hydrogen cylinders.

Claims

1. An autothermal reactor for producing high purity hydrogen from an organic feedstock, a source of oxygen and optionally water comprising a catalyst bed for converting the feedstock into a hydrogen containing gas stream in association with a hydrogen diffusion membrane which selectively separates hydrogen from the other components of the gas stream.
2. A reactor according to claim 1 wherein the catalyst bed and the hydrogen diffusion membrane are located in the same reactor vessel.
3. A reactor according to claim 1 or claim 2 wherein the hydrogen diffusion membrane is a palladium-based membrane, a ceramic membrane or a zeolite membrane.
4. A reactor according to claim 3 wherein the hydrogen diffusion membrane is a palladium based membrane in the form of a coiled or spiral tube.
5. A reactor according to claim 3 wherein the hydrogen diffusion membrane is a palladium-based membrane in the form of a bundle of straight tubes.
6. A reactor according to claim 3 wherein the hydrogen diffusion membrane comprises a thin film of palladium alloy supported on the upstream hydrogen contacting surface of a porous ceramic substrate.
7. A reactor according to claim 6 wherein a methanation catalyst is deposited on the down stream surface of the porous ceramic surface.
8. A reactor according to any one of the preceding claims wherein the catalyst bed comprises a granular bed of catalyst particles.
9. A reactor according to any one of the claims 1 to 7 wherein the catalyst bed comprises a porous ceramic support material coated with the catalyst.
10. A reactor according to any one of claims 1 to 7 wherein the catalyst bed comprises a porous ceramic foam coated with the catalyst.
11. A reactor according to any one of claims 1 to 7 wherein the catalyst bed is in the form of a solid porous foam of the catalyst.
12. A reactor according to any one of the preceding claims wherein the catalyst bed is positioned concentrically and co-axially around the hydrogen diffusion membrane.
13. A reactor according to claim 4 or claim 5 wherein the catalyst bed is in the form of a granular bed of catalyst particles and the palladium based coiled or spiral tube or bundle of straight tubes is buried in the granular bed of catalyst particles.
14. A reactor according to claim 4 wherein the coiled or spiral tube is wrapped around the catalyst bed.
15. A reactor according to any one of the preceding claims wherein the heat generated by the catalytic reaction is used to sustain the operating temperature of the hydrogen diffusion membrane.
16. A reactor according to any one of the preceding claims which operates by a combination of partial oxidation and steam reforming.
17. A reactor according to any one of the preceding claims which operates by a combination of partial oxidation, steam reforming and water gas shift reaction.
18. A reactor according to any one of the preceding claims in which the temperature of the catalytic reaction is about the same or close to the optimum operating temperature of the hydrogen diffusion membrane.
19. A fuel cell system comprising an autothermal hydrogen generation reactor as claimed in any one of claims 1 to 18.
20. A gas chromatography system comprising an autothermal hydrogen generation reactor as claimed in any one of the claims 1 to 18.
PCT/GB1998/003410 1997-11-17 1998-11-17 Hydrogen generator WO1999025649A1 (en)

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EP1138096A1 (en) * 1998-10-14 2001-10-04 Northwest Power Systems, LLC Fuel processing system
US6746650B1 (en) 1999-06-14 2004-06-08 Utc Fuel Cells, Llc Compact, light weight methanol fuel gas autothermal reformer assembly
EP1088786A1 (en) * 1999-10-01 2001-04-04 Volkswagen Aktiengesellschaft Fuel reforming apparatus and reforming process
WO2001025140A1 (en) * 1999-10-05 2001-04-12 Ballard Power Systems Inc. Fuel cell power generation system with autothermal reformer
WO2002002460A2 (en) * 2000-06-29 2002-01-10 Exxonmobil Research And Engineering Company Heat exchanged membrane reactor for electric power generation
WO2002002460A3 (en) * 2000-06-29 2002-05-16 Exxonmobil Res & Eng Co Heat exchanged membrane reactor for electric power generation
DE10040539A1 (en) * 2000-08-18 2002-03-07 Aral Ag & Co Kg Membrane reactor for producing highly pure hydrogen, used in vehicle driven by fuel cell or in domestic heating, involves steam reforming hydrocarbon stream, and is heated by hot conductor in center of reactor
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WO2002062700A3 (en) * 2001-02-07 2002-11-28 Cie D Etudes Des Technologies Method and device for producing hydrogen by partial oxidation of hydrocarbon fuels
FR2820416A1 (en) * 2001-02-07 2002-08-09 Cie D Etudes Des Technologies Method and device for the production of hydrogen by partial oxidation of hydrocarbon fuels
ITSA20080023A1 (en) * 2008-08-08 2010-02-09 Univ Degli Studi Salerno catalytic autothermal reactor with a flat temperature profile for the production of hydrogen from light hydrocarbons
WO2010016027A2 (en) * 2008-08-08 2010-02-11 Universita Degli Studi Di Salerno Autothermic catalytic reactor with flat temperature profile for the production of hydrogen from light hydrocarbons
US20110150726A1 (en) * 2008-08-08 2011-06-23 Vincenzo Palma Autothermic catalytic reactor with flat temperature profile for the production of hydrogen from light hydrocarbons
WO2010016027A3 (en) * 2008-08-08 2010-04-22 Universita Degli Studi Di Salerno Autothermic catalytic reactor with flat temperature profile
WO2012142006A1 (en) * 2011-04-11 2012-10-18 Saudi Arabian Oil Company Catalytic structures for auto thermal steam reforming (atr) of hydrocarbons
WO2012142009A1 (en) * 2011-04-11 2012-10-18 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
US8597383B2 (en) 2011-04-11 2013-12-03 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
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US10093542B2 (en) 2011-04-11 2018-10-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
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