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WO2004024299A1 - Dispositif et procede pour separer de l'hydrogene pratiquement pur contenu dans un flux de gaz hydrogene - Google Patents

Dispositif et procede pour separer de l'hydrogene pratiquement pur contenu dans un flux de gaz hydrogene Download PDF

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Publication number
WO2004024299A1
WO2004024299A1 PCT/DE2003/002902 DE0302902W WO2004024299A1 WO 2004024299 A1 WO2004024299 A1 WO 2004024299A1 DE 0302902 W DE0302902 W DE 0302902W WO 2004024299 A1 WO2004024299 A1 WO 2004024299A1
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Prior art keywords
hydrogen
separation module
gas stream
hydrogen separation
fuel cell
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PCT/DE2003/002902
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German (de)
English (en)
Inventor
Arnold Lamm
Thomas Poschmann
Wolfgang Weger
Norbert Wiesheu
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Daimlerchrysler Ag
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Publication of WO2004024299A1 publication Critical patent/WO2004024299A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/225—Multiple stage diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/145—At least two purification steps in parallel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a device and a method for separating at least almost pure hydrogen from a hydrogen-containing gas stream according to the kind defined in the preambles of claims 1 and 9.
  • Fuel cells can be produced by hydrogen generation devices e.g. can be supplied with hydrogen by reforming hydrocarbons such as methanol, gasoline or diesel.
  • the product gas generated in a reforming process contains hydrogen, carbon monoxide, carbon dioxide and water vapor.
  • the carbon monoxide must be removed for use in the fuel cell, since this gas acts as a catalyst poison and leads to a loss in performance in the fuel cell.
  • membranes have been used for hydrogen separation, which can consist of different materials such as ceramic, glass, polymer or metal.
  • Metal membranes are characterized by high selectivity for hydrogen and high temperature stability, but have comparatively low permeation rates.
  • a large number of membrane cells each with a hydrogen-selective membrane, are used, in which the individual membranes either successively (in series) or side by side (in parallel) the hydrogen-containing reformate gas flows against them.
  • the membrane cells are stacked on top of each other to form a compact hydrogen separation module.
  • Such hydrogen separation modules or membrane modules are described, for example, by DE 198 60 253 Cl or DE 199 20 517 Cl.
  • the documents DE 692 01 942 T2, EP 0 570 185 A2 and EP 0 974 389 A2 each disclose methods and / or devices for generating an almost pure gas for permeation. These devices are constructed so that they can have two separate permeation stages. Immediately after the first permeation stage there is a second permeation stage on the high pressure side, so that the residual gas remaining after the first permeation stage has the desired gas component, e.g. Hydrogen, can be separated. By connecting two permeation stages in series, the yield of the desired pure gas is increased.
  • the desired gas component e.g. Hydrogen
  • the object of the present invention to provide a device and a method for separating virtually pure hydrogen from a hydrogen-containing gas stream, in particular a gas stream from a hydrogen generation device, for operating a fuel cell, with a hydrogen separation module, which allows the highest possible yield of hydrogen with the smallest possible hydrogen separation module.
  • a method according to the invention which is described by the features of the characterizing part of claim 9, also achieves the object of the invention mentioned above.
  • the invention provides for the use of a first hydrogen separation module, by means of which a first portion of hydrogen is separated from the hydrogen-containing gas. The remaining gas stream then arrives again in the at least one further hydrogen separation module. Since the residual gas flow after the first hydrogen separation module still contains at least a few percent of hydrogen, hydrogen is separated off again in the at least one further hydrogen separation module, the individual hydrogen streams being combined according to a further development of the invention according to the hydrogen separation modules.
  • the yield of hydrogen and thus the uti- lization or the efficiency of the hydrogen separation modules increases. Utilization or efficiency is understood to mean the ratio between the amount of hydrogen which is separated by the hydrogen separation module and the amount of hydrogen which is fed to the hydrogen separation module.
  • the cascading of the hydrogen separation modules described can be repeated as often as desired, with the residual gas, the so-called retentate, being passed from one hydrogen separation module into the subsequent hydrogen separation module.
  • the usual hydrogen content of a hydrogen-containing gas stream originating from a hydrogen generation device two to three of the hydrogen separation modules in the serial connection according to the invention are sufficient, particularly also from the point of view of a construction that is as compact as possible.
  • only two hydrogen separation modules will now be dealt with, which, however, is not intended to restrict the invention or the following explanations to exactly this number of hydrogen separation modules.
  • a water gas shift reactor is arranged upstream of the at least one further hydrogen separation module in the flow direction of the residual gas stream.
  • the water gas shift reaction which is known per se and is frequently used in the field of hydrogen generation devices, is used to remove the carbon monoxide present in the residual gas stream, the concentration of which has risen again due to the separation of a large part of the hydrogen contained in the hydrogen-containing gas stream. with water contained in the residual gas stream to convert to carbon dioxide and hydrogen.
  • the hydrogen additionally obtained in this way can then at least partially be separated off, together with the hydrogen still present in the residual gas stream, in the further hydrogen separation module, the total yield of hydrogen increases.
  • a particularly advantageous embodiment of the method according to the invention provides that a pressure of the hydrogen after the first hydrogen separation module is kept below 1.2 bar a (absolute pressure), while the pressure of the hydrogen after the at least one further hydrogen separation module is kept below 0.9 bar a is maintained, the pressure difference between the two hydrogen streams being compensated for by a hydrogen delivery device.
  • the pressure below 1.2 bar a or lower can be achieved, for example, by changing the operating parameters of the fuel cell and, in particular, by dispensing with a jet pump, which is used to return residual hydrogen after flowing through an anode compartment of the fuel cell into the area of the inflowing hydrogen frequently used can be achieved.
  • jet pumps of this type require a pressure of at least 1.3 to 1.5 bar a of the conveying gas stream, which in this case is the pressure from the hydrogen separator. tion module coming hydrogen flow.
  • a low pressure behind the hydrogen separation module can ideally be achieved. This lower pressure in the flow direction behind the hydrogen separation module compared to the prior art allows the utilization or the efficiency of the hydrogen separation module to be increased.
  • the increase in utilization by lowering the pressure level after the hydrogen separation module can be achieved with significantly less energy overall than a comparable increase in utilization by increasing the pressure in the hydrogen-containing gas flowing into the hydrogen separation module, the so-called feed gas.
  • This energy saving occurs particularly in systems in which the hydrogen-containing gas from an autothermal reforming of a hydrocarbon, e.g. Gasoline comes on, because in such systems, in addition to the water and the hydrocarbon, the compressible medium air must also be compressed.
  • a hydrogen delivery device is used after the hydrogen separation module on the hydrogen side, so that a pressure level of less than 0.9 bar a , in particular about 0.8 bar a , in the area between the further hydrogen separation module and the hydrogen delivery device bar a is reached.
  • the yield of hydrogen in the region of the at least one further hydrogen separation module can be increased again, the pressure difference to the hydrogen from the first hydrogen separation module, which are usually below 500 mbar can be compensated for by the hydrogen delivery device.
  • the hydrogen flow which flows to the fuel cell, is usually composed such that approx. 90% of the hydrogen comes from the area of the first hydrogen separation module and only approx. 10% of the hydrogen comes from the area of the further hydrogen separation module.
  • Lowering the pressure behind the least one further hydrogen separation module to a low level that is very favorable for the yield is therefore possible with a comparatively low use of energy. If, in parallel, the pressure downstream of the first hydrogen separation module is not, or at least not, reduced by using larger amounts of energy, there is the possibility of a very high yield of hydrogen with a comparatively low use of parasitic energy.
  • Figure 1 shows an inventive device for separating hydrogen from a hydrogen-containing gas stream.
  • FIG. 2 shows a structure of the device according to FIG. 2 as an integrated component
  • FIG. 3 shows a partial section of the component according to FIG. 3.
  • a device 1 according to the invention is shown in its principle.
  • a first hydrogen separation module 2 can be seen, to which a hydrogen-containing gas, a so-called feed gas, is fed via a line 3.
  • this feed gas can come from any source.
  • the feed gas comes from a hydrogen generation device 4, which is only indicated here.
  • the feed gas is obtained in a manner known per se from a starting material which has carbon and hydrogen, e.g. Gasoline, diesel, methanol or the like.
  • This starting material is converted together with water and optionally with air in a reformer and, if appropriate, in one or more downstream water gas shift stages to give the hydrogen-containing gas or reformate gas.
  • the reformate gas usually contains hydrogen, carbon dioxide, carbon monoxide and residues of water and the starting material.
  • the proportion of hydrogen in the feed gas is around 40% (autothermal reforming) to 65% (steam reforming).
  • the hydrogen generation device 4 is connected via the line 3 coming hydrogen-containing gas stream, a certain proportion of hydrogen, which, based on the available amount of hydrogen in the feed gas, forms the utilization or the efficiency of the first hydrogen separation module 2, is selectively separated from the feed gas.
  • the hydrogen obtained in this way is at least almost pure. It is fed via a line 5 to an anode compartment 6 of a fuel cell 7, which is not shown in its entirety.
  • the hydrogen is usually fed to the anode compartment 6 with an excess of approximately 20 to 50%, so that a gas stream remains after the anode compartment 6, which gas stream is returned in an anode circuit 8 via a conveying device 9 into the region of the hydrogen in front of the anode compartment 6 ,
  • the conveyor 9 is preferably designed as a diaphragm piston pump, but it can be designed in any manner.
  • the conveyor 9 is not a jet pump.
  • a pressure p x of less than 1.2 bar a can be achieved at the outlet of the hydrogen from the first hydrogen separation module 2, whereas the pressure there in the event that a jet pump would be used, should be at least 1.3 to 1.5 bar a due to the system, since otherwise the jet pump would not be able to maintain the volume flow in the anode circuit 8.
  • the 1 also shows a further hydrogen separation module 10, into which the residual gas stream, the so-called retentate, from the first water Substance separation module 2 flows.
  • this residual gas stream in addition to carbon monoxide, carbon dioxide, water and residues of the starting materials for hydrogen production in the hydrogen production device 4, there are still portions of hydrogen.
  • this proportion of hydrogen is approximately 10 to 20% of the hydrogen originally contained in the hydrogen-containing gas stream.
  • the further hydrogen separation module 10 whose surface area of the separation membranes, that is to say its active surface, ideally amounts to approximately 0.1 to 0.3 of the surface area of the separation membranes in the first hydrogen separation module 2, hydrogen is again separated from the residual gas stream.
  • This separated hydrogen is fed to the hydrogen flow from the first hydrogen separation module 2 via a hydrogen delivery device 12 and in the area of a junction 13 with this - and in the exemplary embodiment shown here with the hydrogen flow from the anode circuit 8 - combined to form a hydrogen flow, which then leads to the anode space 6 the fuel cell 7 flows.
  • the hydrogen delivery device 12 compensates for a pressure difference between the two gas flows and ensures a negative pressure P 2 in the region of the exit of the hydrogen from the further hydrogen separation module 10.
  • a low pressure P which in this case, for example, is of the order of 0, has an effect .8 bar a can have a positive effect on the utilization of the further hydrogen separation module 10. The overall utilization or the overall efficiency of the hydrogen separation thus increases.
  • the pressure p_ after the further hydrogen separation module 10 must therefore be raised to the pressure px after the first hydrogen separation module 2 by the hydrogen delivery device.
  • the energy expenditure for operating the hydrogen delivery device 12 is therefore limited within this low volume flow of hydrogen. This in turn has a positive effect on the overall efficiency of a fuel cell system comprising, for example, the device 1, the hydrogen generating device 4, the fuel cell 7 and also required auxiliary units, such as air supply and the like.
  • the hydrogen delivery device 12 can be designed as a diaphragm piston pump, but other delivery means are also conceivable.
  • the advantage in such a diaphragm piston pump lies in its efficiency, which is significantly better than that of a jet pump, and in the fact that no system-related minimum pressure, as for the delivery jet, has to be provided.
  • a very low pressure for example the 0.8 bar a or less mentioned above, can thus be achieved behind the further hydrogen separation module 10 by means of the membrane piston pump.
  • the diaphragm piston pump is robust and very inexpensive. It can also be built very compact, which makes it particularly interesting for use in mobile systems.
  • An alternative embodiment, not shown here, can nevertheless provide a jet pump as a hydrogen delivery device 12, which, however, is designed in such a way that its delivery jet has a significantly higher density and a significantly higher pressure than the hydrogen which it delivers from the area of the further hydrogen separation module 10 , Since the pressure and density of the medium which forms the delivery jet directly influences the result to be achieved by the jet pump, a low pressure of the hydrogen behind the further hydrogen separation module 10 can also be achieved in this way.
  • water in one Pressure of more than 5 bar a especially at about 10 bar a , can be used as a delivery jet.
  • the feed stream reaches, for example, a pump via a pump into the area of the hydrogen delivery device 12, which is then designed as a jet pump.
  • the delivery flow entrains the hydrogen coming from the further hydrogen separation module 10 and generates the desired low pressure in the area between the further hydrogen separation module 10 and the hydrogen delivery device 12 p 2 . If necessary, the water forming the delivery flow is then at least partially separated from the hydrogen-containing material flow in a separator.
  • the device 1 is operated, for example, with a hydrogen-containing gas stream from a hydrogen generation device 4, which works according to the principle of autothermal reforming, then typical concentrations of hydrogen in the feed gas of the order of about 40% achieved.
  • the hydrogen-containing gas stream or feed gas should have a pressure of approximately 10 bar a .
  • the device 1 is constructed such that the active area of the first hydrogen separation module 2 to the further hydrogen separation module 10 is approximately 3: 1. It is operated such that the pressure p x behind the first hydrogen separation module 2 is approximately 1.15 bar a . At a pressure p 2 of approximately 0.8 bar a downstream of the further hydrogen separation module 10, an overall efficiency in the size of 85% to 90% can be achieved. A single hydrogen separation module would only achieve about 80% efficiency under similar conditions for comparison.
  • the anode circuit 8 is just as little necessary for the functioning of the device 1 described in FIG. 1 as for the device 1 described in FIG. 2 However, as with all systems which supply almost pure hydrogen to the anode compartment 6 of the fuel cell 7, irrespective of the source of this hydrogen, it makes sense for the operation of the fuel cell 7.
  • a water gas shift reactor 14 is arranged in the region of the line 11.
  • This water gas shift reactor 14 can e.g. be designed as a high-temperature shift stage in which a water gas shift reaction takes place at temperatures of approximately 350-400 ° C., in which hydrogen and carbon dioxide are produced from water and carbon monoxide.
  • the advantage of such a water gas shift reactor 14 is firstly that the emission of toxic carbon monoxide is reduced by the water gas shift reactor 14.
  • hydrogen is again generated from the carbon monoxide and water present in the residual gas stream, so that a further hydrogen separation module 10 can be offered a higher hydrogen concentration in the residual gas stream.
  • the overall efficiency of the separation of the hydrogen can be determined Increase the hydrogen-containing gas flow by another 2-3% compared to a structure without water gas shift stage 14. This enables a total utilization of the hydrogen separation of over 90% to be achieved even with comparatively little hydrogen in the hydrogen-containing gas stream, e.g. approx. 40% with autothermal reforming. Utilizations of 95-98% can be achieved when used together with a feed gas stream with approx. 65% hydrogen originating from steam reforming.
  • FIG. 2 shows the device 1 in an embodiment with two hydrogen separation modules 2, 10 and a water gas shift reactor 14.
  • the same device 1 can be seen again in FIG. 3 in a partial section.
  • the two hydrogen separation modules 2 and 10 and the water gas shift reactor 14 are integrated in a single component in the construction according to FIGS. 2 and 3.
  • the hydrogen-containing gas stream or feed gas stream flowing in via line 3 first arrives in the first hydrogen separation module 2, in which a large part of the hydrogen in the hydrogen-containing gas stream is separated and through a collector 15, which is only partially shown here, into line 5 and to the junction 13 arrives.
  • the residual gas flow flows after the first hydrogen separation module 2 through the line 11 formed here as a channel into the water gas shift reactor 14.
  • the direction of flow in the water gas shift reactor 14 is approximately perpendicular to the main direction of flow in the first hydrogen separation module 2.
  • a section of the line 11 designed as a channel connects again, which feeds the residual gas stream, which has now been enriched again with hydrogen, to the further hydrogen separation module 10.
  • the flow direction is rotated again by 90 °, so that the further hydrogen separation module 10 has a main flow direction, which is rotated by 180 ° to the main flow direction of the first hydrogen separation module 2.
  • the further hydrogen separation module 10 also has a collector 16, from which the separated hydrogen can flow to the hydrogen delivery device 12. The remaining gas after the further hydrogen separation module 10 then leaves the component in countercurrent to the feed gas.
  • This structure of the two hydrogen separation modules 2, 10 and the water gas shift reactor 14 allows a very space-saving arrangement, which is very compact and, ultimately, can also be realized with comparatively little weight.
  • the flow guidance also ensures that all connections on the component are accessible from one side. This is very inexpensive, particularly when used under tight spatial conditions, as can often be found in mobile systems, during assembly and maintenance.
  • the device 1 and the method for separating hydrogen from a hydrogen-containing gas stream can in principle be used in all types of fuel cell systems, regardless of whether they are in a mobile system, such as a vehicle on land, on water or in the air, be used in a mobile emergency power supply facility or in a stationary system.
  • auxiliary power unit APU
  • the fuel cell system should not be provided - which would also be conceivable - for supplying the mobile system with drive energy, but for the provision of energy for auxiliary and auxiliary units, such as e.g. the vehicle electronics, an air conditioner, a communication device, a navigation device and the like.

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Abstract

L'invention concerne un procédé et un dispositif pour obtenir de l'hydrogène pratiquement pur à partir d'un flux de gaz hydrogéné, notamment à partir du flux de gaz provenant d'une unité de production d'hydrogène, pour faire fonctionner une pile à combustible. A cet effet, on utilise au moins un module de séparation d'hydrogène. Selon l'invention, on utilise au moins un autre module de séparation d'hydrogène, côté gaz résiduel, en aval du premier module de séparation d'hydrogène, pour séparer de nouveau l'hydrogène contenu dans le gaz résiduel, un convertisseur catalytique auxiliaire étant monté en amont du module supplémentaire. Le procédé et/ou le dispositif selon l'invention sont utilisés de préférence dans un générateur d'énergie auxiliaire à base d'une pile à combustible et d'une unité de production d'hydrogène, installé dans un système mobile, notamment dans un véhicule, le champ d'application de l'invention n'étant cependant pas limité à ce domaine.
PCT/DE2003/002902 2002-09-09 2003-09-02 Dispositif et procede pour separer de l'hydrogene pratiquement pur contenu dans un flux de gaz hydrogene WO2004024299A1 (fr)

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DE10241669A DE10241669B4 (de) 2002-09-09 2002-09-09 Vorrichtung und Verfahren zum Abtrennen von nahezu reinem Wasserstoff aus einem wasserstoffhaltigen Gasstrom
DE10241669.9 2002-09-09

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WO2012173483A1 (fr) * 2011-06-16 2012-12-20 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé de production d'hydrogène

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EP2824068A1 (fr) * 2013-07-12 2015-01-14 Shell Internationale Research Maatschappij B.V. Procédé de production d'hydrogène et de dioxyde de carbone

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WO2012173483A1 (fr) * 2011-06-16 2012-12-20 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé de production d'hydrogène
US9776863B2 (en) 2011-06-16 2017-10-03 Stamicarbon B.V. Method for hydrogen production
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DE10241669A1 (de) 2004-03-25

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