EP4363371A1 - Method and device for producing hydrogen from ammonia - Google Patents
Method and device for producing hydrogen from ammoniaInfo
- Publication number
- EP4363371A1 EP4363371A1 EP22731483.8A EP22731483A EP4363371A1 EP 4363371 A1 EP4363371 A1 EP 4363371A1 EP 22731483 A EP22731483 A EP 22731483A EP 4363371 A1 EP4363371 A1 EP 4363371A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonia
- hydrogen
- oxygen
- gas
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 71
- 239000001257 hydrogen Substances 0.000 title claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 77
- 238000005336 cracking Methods 0.000 claims abstract description 67
- 239000001301 oxygen Substances 0.000 claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000003776 cleavage reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 239000003570 air Substances 0.000 description 14
- 239000003546 flue gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- -1 oxygen ions Chemical class 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
-
- 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
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
- C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
- B01D2252/103—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the invention relates to a process for producing a hydrogen product from ammonia, in which an ammonia-containing feedstock is converted using a burner-fired cracking furnace with catalytic support to form a cracked gas containing hydrogen and nitrogen, from which the hydrogen product is separated to obtain a nitrogen-rich residual gas comprising combustible substances , wherein at least part of the residual gas is burned to fire the cracking furnace.
- the invention relates to a device for carrying out the method according to the invention.
- the hydrogen can be made available without releasing carbon dioxide.
- Plants similar to those used today for large-scale synthesis gas production by steam reforming of hydrocarbons can be used to produce hydrogen from ammonia at higher rates.
- Plants of this type include a cracking furnace with a combustion chamber in which cracking tubes filled with catalyst material are arranged, as well as a waste heat system.
- the combustion chamber is heated by one or more burners, the energy for the endothermic cracking of the ammonia that is passed through the cracking tubes delivery.
- the flue gases generated by the burners can only give off a small part of their sensible heat to the cans, so that they leave the combustion chamber at a high temperature and with a large amount of residual heat.
- the hot flue gases and the hot cracked gas flowing out of the cracking tubes are used to preheat input materials such as ammonia and burner air and, if necessary, to generate steam. Since no or only very little steam can be used in the process itself when splitting ammonia, the steam generated is either exported or - for example via an "Organic Rankine Cycle" - used to generate electricity.
- the ammonia splitting is expediently carried out at pressures of between 10 and 40 bar. This is all the more easily possible as the pressure of the feedstock, which usually is present in liquid form and contains ammonia, can be increased with little expenditure of energy.
- the cracked gas consists largely of hydrogen and nitrogen, but also contains unreacted ammonia and possibly water that is already present in the ammonia-containing feedstock or is additionally introduced into the cracking tubes as a temperature moderator, but does not take part in the cracking reaction.
- the cracked gas is fed to a separation device in which, after the majority of the unreacted ammonia has been removed and the water contained has been separated off, it is preferably treated by pressure swing adsorption, with a largely nitrogen-free hydrogen fraction and a largely nitrogen-containing fraction and ammonia contained residual gas are generated. While the hydrogen fraction can be discharged as product, the tail gas is recycled and combusted to fire the cracking furnace using air as the oxidant. Due to its high nitrogen content, the calorific value of the residual gas is comparatively low, so that additional fuel, such as ammonia, may have to be fired in order to heat the cracking furnace. In addition, the high nitrogen content causes very large amounts of flue gas, the residual heat of which can only be used by using correspondingly large and expensive heat exchangers in the waste heat system.
- the object of the present invention is to specify a method and a device of the generic type which allow hydrogen to be produced from ammonia more economically than is possible according to the prior art.
- an oxygen-rich material flow is supplied from an oxygen source and used as an oxidizing agent directly or after the admixture of air during the combustion of the residual gas.
- a material flow that consists of more than 25% oxygen is considered to be oxygen-rich. However, it preferably has a higher oxygen content of, for example, more than 99%.
- the oxidizing agent used according to the invention has a lower proportion of nitrogen than air, both the fuel requirement required for heating the cracking furnace and the amount of flue gas generated are reduced compared to the prior art.
- the waste heat system can therefore be run more cost-effectively with smaller heat exchangers or—if, for example, steam generation can be omitted—fewer heat exchangers. Because of its high nitrogen content, it is possible to burn the residual gas independently of the oxygen content of the oxidizing agent used using conventional burners, such as those used for residual gas combustion with air.
- the oxygen source can be, for example, a cryogenic air separator. It is also conceivable to use an electrolyser as the source of oxygen, which electrochemically breaks down water and generates a stream of hydrogen and an oxygen-rich substance. While at least part of the oxygen-rich stream directly or after the admixture of air as Oxidizing agent is used in the combustion of the residual gas, the hydrogen-rich stream can be used as fuel to fire the cracking furnace and / or to supplement the amount of hydrogen produced by the ammonia cracking.
- the electrolyser can generate the two material flows with the same or different pressures.
- both the oxygen-rich and the hydrogen-rich substance flow are generated at a pressure which is sufficiently high to be able to feed each of the two substance flows to their further use without the use of a compressor.
- the separation of hydrogen from the cracked gas obtained in the cracking furnace takes place in a separating device which supplies a hydrogen fraction which can be released as a product as well as the residual gas which is rich in nitrogen and comprises combustible substances.
- the hydrogen-rich stream produced by the electrolyzer can be admixed with the hydrogen fraction downstream of the separating device directly or after removal of water and other impurities.
- An advantageous embodiment of the method according to the invention provides that the electrolyzer is operated in such a way that the amount of oxygen produced is always as large as the instantaneous oxygen requirement of the cracking furnace. If it is not possible to adapt the oxygen output of the electrolyser quickly enough to the oxygen demand of the cracking furnace, excess oxygen produced can be transferred to an intermediate store, while the lack of oxygen can be removed from the
- Cache is removed and / or compensated by the supply of ambient air.
- the electrolyzer used according to the invention can comprise a solid oxide electrolytic cell which operates at high temperatures between 500°C and 950°C water vapor splits.
- an electrolyte consisting of a material that is conductive to oxygen ions separates a cathode space from an anode space. Water vapor introduced into the cathode compartment is split at the interface with the electrolyte into hydrogen, which remains on the cathode side, and oxygen ions, which migrate to the anode side, where they are oxidized to form oxygen molecules.
- the anode chamber is purged with air.
- the solid oxide electrolytic cell therefore provides a hot oxygenate stream which is oxygen-enriched air.
- the oxygen-containing stream is preferably used without further treatment—in particular without cooling—to form the oxidizing agent according to the invention.
- the electrolyte in another electrolytic cell which can be used according to the invention and which is operated at comparably high temperatures, the electrolyte consists of a ceramic proton-conducting membrane at which water supplied in vapor form on the anode side is split. While the resulting hydrogen ions diffuse to the cathode side and are drawn off in a dry stream after the formation of hydrogen molecules, a water-containing, oxygen-rich substance stream is produced at the anode.
- electrolytic cells which can be operated at lower temperatures and which are known to those skilled in the art as proton exchange, anion exchange or alkaline electrolytic cells are also suitable for use according to the invention.
- part of the ammonia used is always not converted and ends up unchanged in the cracked gas, from which it has to be separated to obtain a hydrogen product.
- the amount of unreacted ammonia increases as the reaction temperature decreases and the reaction pressure increases.
- the ammonia content of the cracked gas is low, the ammonia is preferably separated off solely by pressure swing adsorption and thermally utilized with the residual gas. With a higher ammonia content, however, it can be more economical to also remove ammonia from the cracked gas upstream of the pressure swing adsorption and to utilize it materially.
- the method according to the invention it is proposed to cool the cracked gas to below the water dew point, so that water condenses and ammonia is washed out of the cracked gas by the condensed water. If the cracked gas is cooled to temperatures between 30°C and 70°C, the amount of water fed into the cracking tubes together with the ammonia as a temperature moderator is sufficient to reduce the ammonia content to such an extent that the part of the ammonia remaining in the cracked gas can be removed without economic Disadvantages can be separated by the pressure swing adsorption. A separate supply of washing water is not necessary, at least in normal operation.
- the ammonia/water mixture obtained in the water wash is preferably reused in the cracking furnace, with most of the mixture being fed into the cracking tubes to produce hydrogen and the remaining part being discharged in a controlled manner to adjust the amount of water introduced into the cracking tubes and used, for example, to fire the cracking furnace will.
- the invention provides for water to be additionally supplied to the water wash from the outside.
- the cracking tubes will be cooled with steam or nitrogen.
- one embodiment of the process according to the invention provides for the hot cracked gas obtained in the cracking furnace to be used to heat a cracking reactor in which a further cracked gas is formed by cracking ammonia into hydrogen and nitrogen.
- the cracked gas formed in the cracking reactor from part or all of the ammonia-containing feedstock is either further treated in the cracking tubes of the cracking furnace or combined with the cracked gas cooled during heating of the cracking reactor.
- the invention relates to a device for producing a hydrogen product from ammonia, with a cracking furnace comprising at least one burner for the catalytically supported conversion of an ammonia-containing feedstock into a cracked gas containing hydrogen and nitrogen, a separating device with which hydrogen is separated from the cracked gas while obtaining a nitrogen-rich, combustible substances can be separated comprehensive residual gas, as well as a recirculation device, through which at least part of the residual gas can be returned to be burned over the at least one burner for firing the cracking furnace.
- a cracking furnace comprising at least one burner for the catalytically supported conversion of an ammonia-containing feedstock into a cracked gas containing hydrogen and nitrogen, a separating device with which hydrogen is separated from the cracked gas while obtaining a nitrogen-rich, combustible substances can be separated comprehensive residual gas, as well as a recirculation device, through which at least part of the residual gas can be returned to be burned over the at least one burner for firing the cracking furnace.
- the stated object is achieved according to the invention in that the device comprises an oxygen source connected to the at least one burner, from which an oxygen-rich material flow can be taken and used as an oxidizing agent directly or after the admixture of air in the combustion of the residual gas.
- the source of oxygen is an electrolyzer capable of electrochemically breaking down water and producing a stream of hydrogen and an oxygen-rich stream.
- the electrolyser may comprise a solid oxide electrolytic cell capable of splitting water vapor at operating temperatures between 500°C and 850°C and producing a hot, oxygen-rich stream of material.
- the separating device preferably comprises a pressure swing adsorber which is able to separate from the cracked gas a hydrogen fraction which can be released as a product due to its purity and pressure and to feed it to a consumer via a product gas line. Nitrogen and also ammonia present in the cracked gas can be removed from the pressure swing adsorber as residual gas.
- the electrolyser serving as the oxygen source is expediently connected not only to the at least one burner of the cracking furnace, but also to the separating device, so that the hydrogen-rich material flow that can be generated by the electrolyser can be used to reduce the quantity of the hydrogen fraction that is generated by the ammonia cracking and can be specified as a product to complete.
- the separation of Impurities between the electrolyzer and the separator may be arranged a cleaning device.
- the electrolyzer can be connected to the separating device upstream of the pressure swing adsorber, so that impurities contained in the hydrogen-rich substance stream can be removed by the pressure swing adsorber.
- the separation of nitrogen and ammonia from the cracked gas can be carried out economically using a pressure swing adsorber. It makes sense then that the cracked gas upstream of the pressure swing adsorber is not cooled down to the dew point in order to prevent liquid from entering the pressure swing adsorber.
- the device according to the invention can be designed, for example, with an adjustable air cooler for controlled cracked gas cooling. If the ammonia content of the cracked gas is above the limit value, it is proposed to arrange a water scrubber upstream of the pressure swing adsorber, which is sensibly capable of washing out ammonia and reducing the ammonia content of the cracked gas to below the limit value, forming an ammonia/water mixture. Furthermore, it is proposed to connect the water wash with the cracking furnace in such a way that at least part of the ammonia/water mixture can be fed back into the cracking tubes.
- the water scrubbing is preferably carried out with a cooling device, via which the cracked gas can be cooled to below the water dew point, so that water can condense and ammonia can be washed out of the cracked gas by the condensed water.
- the water scrubbing is particularly preferably carried out without a supply device for additional scrubbing water and a cooling device which is able to cool the cracked gas down to temperatures between 30.degree. C. and 70.degree.
- the device according to the invention can comprise a cracking reactor connected to the cracking furnace for cracking ammonia, which can be heated by hot cracking gas available in the cracking furnace.
- a cracking reactor connected to the cracking furnace for cracking ammonia, which can be heated by hot cracking gas available in the cracking furnace.
- FIG. 1 shows the production of hydrogen from ammonia according to a preferred embodiment of the invention, in which an electrolyzer with a solid oxide electrolytic cell serves as the oxygen source.
- An input material consisting largely of ammonia and containing water is fed to the cracking furnace S via line 1 and introduced into the cracking tubes R, which are heated with heat 2 generated by the burner B.
- the majority of the ammonia supplied is cracked at temperatures between 500 and 1000° C., so that a hot cracked gas 3, consisting largely of nitrogen and hydrogen, containing water and unreacted ammonia, can be removed from the cracking tubes R and transferred to the separating device T .
- a hot cracked gas 3 consisting largely of nitrogen and hydrogen, containing water and unreacted ammonia
- the cracked gas 3 is cooled to temperatures between 30° C. and 70° C., with water condensing out and washing out a large part of the ammonia.
- the cracked gas 5 which is largely free of water and ammonia, is fed into the pressure swing adsorber D, where it is divided into a product-pure hydrogen fraction 6 and a residual gas 7 is separated.
- the residual gas 7 which mainly consists of nitrogen but also contains combustible components such as ammonia and hydrogen, is fed to the burner B as fuel and burned together with the oxidizing agent 8 .
- the residual heat of the flue gases 15 of the burner B, which have been cooled against the cracking tubes R, is used in a waste heat system (not shown), for example for evaporating and preheating the feedstock 1 .
- the oxidizing agent 8 which has a higher oxygen content than air, is taken out from the electrolyzer E functioning as an oxygen source.
- the electrolyser E which includes a solid oxide electrolytic cell, splits water vapor at operating temperatures between 500°C and 950°C.
- an electrolyte M consisting of a material that is conductive for oxygen ions separates a cathode K from an anode compartment A remains, and oxygen ions are split, which migrate to the anode side, where they are oxidized to oxygen molecules.
- the anode chamber A is flushed with air 10, the hot oxidizing agent 8 being produced, which is fed to the burner B without cooling. From the cathode compartment K, a hydrogen-rich stream 11 is withdrawn and with the product purity having hydrogen fraction 6 to
- the burner B can be supplied with air 13 as a further oxidizing agent and/or ammonia 14 as an additional fuel.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to a method and a device for producing a hydrogen product (6) from ammonia. An ammonia-containing feed material (1) is converted into a cracked gas (3), which contains hydrogen and nitrogen, using a burner-fired cracking furnace (S) with a catalytic support, said hydrogen product (6) being separated from the cracked gas, thereby obtaining a nitrogen-enriched remaining gas (7) which comprises combustible materials, wherein at least one part of the remaining gas (7) is combusted in order to fire the cracking furnace (S). The invention is characterized in that an oxygen-enriched material flow (8) is supplied from an oxygen source (E) and is used as an oxidizing agent immediately or after adding air (13) while combusting the remaining gas (7).
Description
Beschreibung description
Verfahren und Vorrichtung zur Erzeugung von Wasserstoff aus Ammoniak Process and device for producing hydrogen from ammonia
Die Erfindung betrifft ein Verfahren zur Erzeugung eines Wasserstoffprodukts aus Ammoniak, wobei ein Ammoniak enthaltender Einsatzstoff unter Verwendung eines brennerbefeuerten Spaltofens mit katalytischer Unterstützung zu einem Wasserstoff und Stickstoff enthaltenden Spaltgas umgesetzt wird, von dem das Wasserstoffprodukt unter Erhalt eines stickstoffreichen, brennbare Stoffe umfassenden Restgases abgetrennt wird, wobei zumindest ein Teil des Restgases zur Befeuerung des Spaltofens verbrannt wird. The invention relates to a process for producing a hydrogen product from ammonia, in which an ammonia-containing feedstock is converted using a burner-fired cracking furnace with catalytic support to form a cracked gas containing hydrogen and nitrogen, from which the hydrogen product is separated to obtain a nitrogen-rich residual gas comprising combustible substances , wherein at least part of the residual gas is burned to fire the cracking furnace.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Durchführung des erfindungsgemäßen Verfahrens. Furthermore, the invention relates to a device for carrying out the method according to the invention.
Die Erzeugung von Wasserstoff durch katalytisch unterstütze Spaltung von Ammoniak ist bekannt und seit vielen Jahren Stand der Technik. Die dabei ablaufende ReaktionThe generation of hydrogen by catalytically assisted cracking of ammonia is known and has been state of the art for many years. The reaction taking place
2NH3 <-» N2 + 3H2 ist endotherm (DH=46, 2 kJ/mol). Die Lage des Gleichgewichts und die Reaktionsgeschwindigkeit hängen stark von Druck und Temperatur sowie von der Art des eingesetzten Katalysators ab. 2NH 3 < -» N 2 + 3H 2 is endothermic (DH=46.2 kJ/mol). The position of the equilibrium and the reaction rate depend strongly on the pressure and temperature and on the type of catalyst used.
Insbesondere für industrielle Anwendungen mit vergleichsweise geringem Wasserstoffbedarf von weniger als 1000mn 3/h, wie beispielsweise für die Wärmebehandlung von Metallen, ist die Ammoniakspaltung mit Hilfe elektrisch beheizter Spaltöfen wirtschaftlich vorteilhaft. Prinzipiell kann der Wasserstoff hierbei ohne Freisetzung von Kohlendioxid zur Verfügung gestellt werden. In particular for industrial applications with a comparatively low hydrogen requirement of less than 1000m n 3 /h, such as for the heat treatment of metals, cracking ammonia using electrically heated cracking furnaces is economically advantageous. In principle, the hydrogen can be made available without releasing carbon dioxide.
Um Wasserstoff aus Ammoniak mit höheren Raten herzustellen, können ähnliche Anlagen eingesetzt werden, wie sie heute zur großtechnischen Synthesegaserzeugung durch Dampfreformierung von Kohlenwasserstoffen verwendet werden. Derartige Anlagen umfassen einen Spaltofen mit einem Feuerraum, in dem mit Katalysatormaterial gefüllte Spaltrohre angeordnet sind, sowie ein Abhitzesystem. Der Feuerraum wird durch einen oder mehrere Brenner beheizt, die Energie für die endotherm ablaufende Spaltung des durch die Spaltrohre geführten Ammoniaks
liefern. Die von den Brennern erzeugten Rauchgase können hierbei nur einen kleinen Teil ihrer fühlbaren Wärme an die Spaltrohre abgeben, so dass sie den Feuerraum mit hoher Temperatur und einem großen Inhalt an Restwärme verlassen. Um die Wasserstofferzeugung effizient durchführen zu können, werden die heißen Rauchgase ebenso wie das heiß aus den Spaltrohren strömende Spaltgas zur Vorwärmung von Einsatzstoffen wie Ammoniak und Brennerluft sowie ggf. zur Dampferzeugung genutzt. Da bei der Ammoniakspaltung kein oder nur sehr wenig Dampf im Prozess selbst eigesetzt werden kann, wird der erzeugte Dampf entweder exportiert oder- beispielsweise über einen „Organic Rankine Cycle“ - zur Stromerzeugung verwendet. Plants similar to those used today for large-scale synthesis gas production by steam reforming of hydrocarbons can be used to produce hydrogen from ammonia at higher rates. Plants of this type include a cracking furnace with a combustion chamber in which cracking tubes filled with catalyst material are arranged, as well as a waste heat system. The combustion chamber is heated by one or more burners, the energy for the endothermic cracking of the ammonia that is passed through the cracking tubes delivery. The flue gases generated by the burners can only give off a small part of their sensible heat to the cans, so that they leave the combustion chamber at a high temperature and with a large amount of residual heat. In order to be able to produce hydrogen efficiently, the hot flue gases and the hot cracked gas flowing out of the cracking tubes are used to preheat input materials such as ammonia and burner air and, if necessary, to generate steam. Since no or only very little steam can be used in the process itself when splitting ammonia, the steam generated is either exported or - for example via an "Organic Rankine Cycle" - used to generate electricity.
Damit der erzeugte Wasserstoff ohne oder mit nur geringem Verdichtungsaufwand als Produkt abgegeben werden kann, wird die Ammoniakspaltung zweckmäßigerweise bei Drücken zwischen 10 und 40 bar durchgeführt. Dies ist umso einfacher möglich, als der Druck des gewöhnlich flüssig vorliegenden Ammoniak enthaltenden Einsatzstoffs mit wenig Energieaufwand erhöht werden kann. Damit unter diesen Bedingungen ein ausreichend hoher, wirtschaftlich sinnvoller Umsetzungsgrad des eingesetzten Ammoniaks erreicht wird, ist es notwendig, die Spaltung bei Temperaturen zwischen 500 und 1000°C zu betreiben. Das Spaltgas besteht zu einem großen Teil aus Wasserstoff und Stickstoff, enthält daneben aber auch nicht umgesetztes Ammoniak sowie evtl. Wasser, das bereits in dem Ammoniak enthaltenden Einsatzstoff vorliegt bzw. zusätzlich als Temperaturmoderator in die Spaltrohre eingeleitet wird, jedoch nicht an der Spaltreaktion teilnimmt. So that the hydrogen produced can be released as a product with little or no compression, the ammonia splitting is expediently carried out at pressures of between 10 and 40 bar. This is all the more easily possible as the pressure of the feedstock, which usually is present in liquid form and contains ammonia, can be increased with little expenditure of energy. In order to achieve a sufficiently high, economically viable degree of conversion of the ammonia used under these conditions, it is necessary to operate the cleavage at temperatures between 500 and 1000.degree. The cracked gas consists largely of hydrogen and nitrogen, but also contains unreacted ammonia and possibly water that is already present in the ammonia-containing feedstock or is additionally introduced into the cracking tubes as a temperature moderator, but does not take part in the cracking reaction.
Zur Gewinnung des Wasserstoffs wird das Spaltgas einer Trenneinrichtung zugeführt, in der es nach der Entfernung des überwiegenden Teils des nicht umgesetzten Ammoniaks und der Abtrennung von enthaltenem Wasser vorzugsweise durch Druckwechseladsorption behandelt wird, wobei eine weitgehend stickstofffreie Wasserstofffraktion sowie ein zum Großteil aus Stickstoff bestehendes und Ammoniak enthaltendes Restgas erzeugt werden. Während die Wasserstofffraktion als Produkt abgegeben werden kann, wird das Restgas zurückgeführt und zur Befeuerung des Spaltofens unter Verwendung von Luft als Oxidationsmittel verbrannt.
Aufgrund seines hohen Stickstoffanteils ist der Heizwert des Restgases vergleichsweise gering, so dass zur Beheizung des Spaltofens u.U. weiterer Brennstoff, wie z.B. Ammoniak, zugefeuert werden muss. Darüber hinaus bedingt der hohe Stickstoffanteil sehr große Rauchgasmengen, deren Restwärme nur durch den Einsatz entsprechend großer und teurer Wärmetauscher im Abhitzesystem genutzt werden kann. To obtain the hydrogen, the cracked gas is fed to a separation device in which, after the majority of the unreacted ammonia has been removed and the water contained has been separated off, it is preferably treated by pressure swing adsorption, with a largely nitrogen-free hydrogen fraction and a largely nitrogen-containing fraction and ammonia contained residual gas are generated. While the hydrogen fraction can be discharged as product, the tail gas is recycled and combusted to fire the cracking furnace using air as the oxidant. Due to its high nitrogen content, the calorific value of the residual gas is comparatively low, so that additional fuel, such as ammonia, may have to be fired in order to heat the cracking furnace. In addition, the high nitrogen content causes very large amounts of flue gas, the residual heat of which can only be used by using correspondingly large and expensive heat exchangers in the waste heat system.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren und eine Vorrichtung der gattungsgemäßen Art anzugeben, die es erlauben, Wasserstoff aus Ammoniak wirtschaftlicher zu erzeugen, als es nach dem Stand der Technik möglich ist. The object of the present invention is to specify a method and a device of the generic type which allow hydrogen to be produced from ammonia more economically than is possible according to the prior art.
Die gestellt Aufgabe wird verfahrensseitig erfindungsgemäß dadurch gelöst, dass aus einer Sauerstoffquelle ein sauerstoffreicher Stoffstrom zugeführt und direkt oder nach Zumischung von Luft bei der Verbrennung des Restgases als Oxidationsmittel eingesetzt wird. The stated object is achieved according to the invention in that an oxygen-rich material flow is supplied from an oxygen source and used as an oxidizing agent directly or after the admixture of air during the combustion of the residual gas.
Als sauerstoffreich gilt im Rahmen der vorliegenden Erfindung ein Stoffstrom, der zu mehr als 25% aus Sauerstoff besteht. Bevorzugt weist er jedoch einen höheren Sauerstoffgehalt von beispielsweise mehr als 99% auf. In the context of the present invention, a material flow that consists of more than 25% oxygen is considered to be oxygen-rich. However, it preferably has a higher oxygen content of, for example, more than 99%.
Da das erfindungsgemäß eingesetzte Oxidationsmittel einen geringeren Stickstoffanteil als Luft besitzt, reduzieren sich gegenüber dem Stand der Technik sowohl der für die Beheizung des Spaltofens benötigte Brennstoffbedarf als auch die erzeugte Rauchgasmenge. Zur Nutzung der Restwärme des Rauchgases kann das Abhitzesystem daher kostengünstiger mit kleineren bzw. - wenn beispielsweise eine Dampferzeugung entfallen kann - weniger Wärmetauschern ausgeführt werden. Wegen seines hohen Stickstoffgehalts ist es möglich, das Restgas unabhängig vom Sauerstoffgehalt des eingesetzten Oxidationsmittels über konventionelle Brenner zu verfeuern, wie sie auch zur Restgasverfeuerung mit Luft eingesetzt werden. Since the oxidizing agent used according to the invention has a lower proportion of nitrogen than air, both the fuel requirement required for heating the cracking furnace and the amount of flue gas generated are reduced compared to the prior art. In order to use the residual heat of the flue gas, the waste heat system can therefore be run more cost-effectively with smaller heat exchangers or—if, for example, steam generation can be omitted—fewer heat exchangers. Because of its high nitrogen content, it is possible to burn the residual gas independently of the oxygen content of the oxidizing agent used using conventional burners, such as those used for residual gas combustion with air.
Bei der Sauerstoffquelle kann es sich beispielsweise um einen kryogenen Luftzerleger handeln. Denkbar ist es auch, als Sauerstoffquelle einen Elektrolyseur einzusetzen, der Wasser elektrochemisch zerlegt und einen Wasserstoff- sowie einen sauerstoffreichen Stoffstrom erzeugt. Während zumindest ein Teil des sauerstoffreichen Stoffstroms direkt oder nach Zumischung von Luft als
Oxidationsmittel bei der Verbrennung des Restgases eingesetzt wird, kann der wasserstoffreiche Stoffstrom als Brennstoff zur Befeuerung des Spaltofens und/oder zur Ergänzung der Menge des durch die Ammoniakspaltung erzeugten Wasserstoffs verwendet werden. Der Elektrolyseur kann die beiden Stoffströme mit gleichen oder unterschiedlichen Drücken erzeugen. Zweckmäßigerweise wird sowohl der sauerstoff- als auch der wasserstoffreiche Stoffstrom mit einem Druck erzeugt, der ausreichend hoch ist, um jeden der beiden Stoffströme ohne den Einsatz eines Verdichters ihrer weiteren Verwendung zuführen zu können. Die Abtrennung von Wasserstoff aus dem im Spaltofen erhaltenen Spaltgas erfolgt in einer Trenneinrichtung, die eine als Produkt abgebbare Wasserstofffraktion sowie das stickstoffreiche, brennbare Stoffe umfassende Restgas liefert. Zur Erhöhung der durch Ammoniakspaltung erzeugten Wasserstoffmenge, kann der wasserstoffreiche, durch den Elektrolyseur erzeugte Stoffstrom der Wasserstofffraktion stromabwärts der Trenneinrichtung direkt oder nach Entfernung von Wasser und anderen Verunreinigungen zugemischt werden. Möglich ist es aber auch, den wasserstoffreichen Stoffstrom aus dem Elektrolyseur in die Trenneinrichtung zu überführen und gemeinsam mit dem Spaltgas zu der als Produkt abgebbaren Wasserstofffraktion aufzubereiten. The oxygen source can be, for example, a cryogenic air separator. It is also conceivable to use an electrolyser as the source of oxygen, which electrochemically breaks down water and generates a stream of hydrogen and an oxygen-rich substance. While at least part of the oxygen-rich stream directly or after the admixture of air as Oxidizing agent is used in the combustion of the residual gas, the hydrogen-rich stream can be used as fuel to fire the cracking furnace and / or to supplement the amount of hydrogen produced by the ammonia cracking. The electrolyser can generate the two material flows with the same or different pressures. Expediently, both the oxygen-rich and the hydrogen-rich substance flow are generated at a pressure which is sufficiently high to be able to feed each of the two substance flows to their further use without the use of a compressor. The separation of hydrogen from the cracked gas obtained in the cracking furnace takes place in a separating device which supplies a hydrogen fraction which can be released as a product as well as the residual gas which is rich in nitrogen and comprises combustible substances. In order to increase the amount of hydrogen produced by splitting ammonia, the hydrogen-rich stream produced by the electrolyzer can be admixed with the hydrogen fraction downstream of the separating device directly or after removal of water and other impurities. However, it is also possible to transfer the hydrogen-rich substance stream from the electrolyzer into the separating device and to process it together with the cracked gas to form the hydrogen fraction that can be released as a product.
In Spuren vorliegender Wasserstoff kann im sauerstoffreichen Stoffstrom des Elektrolyseurs belassen werden, da er den Heizwert der dem Spaltofen insgesamt zugeführten Brennstoffe erhöht und so die erzeugte Rauchgasmenge verringert. Eine vorteilhafte Ausgestaltung des erfindungsgemäßen Verfahrens sieht vor, dass der Elektrolyseur so betrieben wird, dass die Menge des produzierten Sauerstoffs stets so groß ist, wie der momentane Sauerstoffbedarf des Spaltofens. Falls es nicht möglich ist, die Sauerstoff-Leistung des Elektrolyseurs schnell genug an dem Sauerstoffbedarf des Spaltofens anzupassen, kann überschüssig produzierter Sauerstoff in einen Zwischenspeicher überführt werden, während fehlender Sauerstoff aus demTraces of hydrogen can be left in the oxygen-rich material flow of the electrolyser, since it increases the calorific value of the fuels fed to the cracking furnace as a whole and thus reduces the amount of flue gas produced. An advantageous embodiment of the method according to the invention provides that the electrolyzer is operated in such a way that the amount of oxygen produced is always as large as the instantaneous oxygen requirement of the cracking furnace. If it is not possible to adapt the oxygen output of the electrolyser quickly enough to the oxygen demand of the cracking furnace, excess oxygen produced can be transferred to an intermediate store, while the lack of oxygen can be removed from the
Zwischenspeicher entnommen und/oder durch die Zuführung von Umgebungsluft ausgeglichen wird. Cache is removed and / or compensated by the supply of ambient air.
Der erfindungsgemäß eingesetzte Elektrolyseur kann eine Festoxid-Elektrolysezelle umfassen, die bei hohen Betriebstemperaturen zwischen 500°C und 950°C
Wasserdampf spaltet. In der Elektrolysezelle trennt ein aus einem für Sauerstoffionen leitfähigen Material bestehender Elektrolyt einen Kathoden- von einem Anodenraum. In den Kathodenraum eingebrachter Wasserdampf wird an der Grenzfläche zum Elektrolyten in Wasserstoff, der auf der Kathodenseite verbleibt, und Sauerstoffionen gespalten, die zur Anodenseite wandern, wo sie zu Sauerstoffmolekülen oxidiert werden. Um den Sauerstoffpartialdruck gering zu halten und die verbauten Materialien vor Oxidation zu schützen, wird der Anodenraum mit Luft gespült. Die Festoxid- Elektrolysezelle liefert daher einen heißen sauerstoffhaltigen Stoffstrom, bei dem es sich um mit Sauerstoff angereicherte Luft handelt. Vorzugsweise wird der sauerstoffhaltige Stoffstrom ohne weitere Behandlung - insbesondere ohne Abkühlung - zur erfindungsgemäßen Bildung des Oxidationsmittels eingesetzt. The electrolyzer used according to the invention can comprise a solid oxide electrolytic cell which operates at high temperatures between 500°C and 950°C water vapor splits. In the electrolytic cell, an electrolyte consisting of a material that is conductive to oxygen ions separates a cathode space from an anode space. Water vapor introduced into the cathode compartment is split at the interface with the electrolyte into hydrogen, which remains on the cathode side, and oxygen ions, which migrate to the anode side, where they are oxidized to form oxygen molecules. In order to keep the oxygen partial pressure low and to protect the installed materials from oxidation, the anode chamber is purged with air. The solid oxide electrolytic cell therefore provides a hot oxygenate stream which is oxygen-enriched air. The oxygen-containing stream is preferably used without further treatment—in particular without cooling—to form the oxidizing agent according to the invention.
In einer anderen erfindungsgemäß einsetzbaren Elektrolysezelle, die bei vergleichbar hohen Temperaturen betrieben wird, besteht der Elektrolyt aus einer keramischen protonenleitenden Membran, an der anodenseitig dampfförmig zugeführtes Wasser gespalten wird. Während die hierbei entstehenden Wasserstoffionen zur Kathodenseite diffundieren und nach der Bildung von Wasserstoffmolekülen in einem trockenen Strom abgezogen werden, entsteht an der Anode ein wasserhaltiger sauerstoffreicher Stoffstrom. In another electrolytic cell which can be used according to the invention and which is operated at comparably high temperatures, the electrolyte consists of a ceramic proton-conducting membrane at which water supplied in vapor form on the anode side is split. While the resulting hydrogen ions diffuse to the cathode side and are drawn off in a dry stream after the formation of hydrogen molecules, a water-containing, oxygen-rich substance stream is produced at the anode.
Weitere, bei niedrigeren Temperaturen betreibbare Elektrolysezellen, die dem Fachmann als Protonen-Austausch-, Anionen-Austausch- oder alkalische Elektrolysezellen bekannt sind, eignen sich ebenfalls für den erfindungsgemäßen Einsatz. Other electrolytic cells which can be operated at lower temperatures and which are known to those skilled in the art as proton exchange, anion exchange or alkaline electrolytic cells are also suitable for use according to the invention.
Bei der Ammoniakspaltung wird stets ein Teil des eingesetzten Ammoniaks nicht umgesetzt und gelangt unverändert in das Spaltgas, aus dem es zum Erhalt eines Wasserstoffprodukts abgetrennt werden muss. Die Menge des nicht umgesetzten Ammoniaks erhöht sich mit sinkender Reaktionstemperatur und steigendem Reaktionsdruck. Ist der Ammoniakgehalt des Spaltgases gering, wird das Ammoniak vorzugsweise allein durch Druckwechseladsorption abgetrennt und mit dem Restgas thermisch verwertet. Bei höheren Ammoniakgehalt kann es allerdings wirtschaftlicher sein, Ammoniak zusätzlich stromaufwärts der Druckwechseladsorption aus dem Spaltgas zu entfernen und stofflich zu verwerten.
Das erfindungsgemäße Verfahren weiterbildend wird vorgeschlagen, das Spaltgas bis unter den Wassertaupunkt abzukühlen, so dass Wasser kondensiert und Ammoniak durch das kondensierte Wasser aus dem Spaltgas ausgewaschen wird. Wenn das Spaltgas auf Temperaturen zwischen 30°C und 70°C abgekühlt wird, reicht die Menge des als Temperaturmoderator zusammen mit dem Ammoniak in die Spaltrohre eingeleiteten Wassers aus, um den Ammoniakgehalt soweit zu reduzieren, dass der im Spaltgas verbleibende Teil des Ammoniaks ohne wirtschaftliche Nachteile durch die Druckwechseladsorption abgetrennt werden kann. Eine gesonderte Zuführung von Waschwasser ist zumindest im Normalbetrieb nicht notwendig. In the cracking of ammonia, part of the ammonia used is always not converted and ends up unchanged in the cracked gas, from which it has to be separated to obtain a hydrogen product. The amount of unreacted ammonia increases as the reaction temperature decreases and the reaction pressure increases. If the ammonia content of the cracked gas is low, the ammonia is preferably separated off solely by pressure swing adsorption and thermally utilized with the residual gas. With a higher ammonia content, however, it can be more economical to also remove ammonia from the cracked gas upstream of the pressure swing adsorption and to utilize it materially. Developing the method according to the invention, it is proposed to cool the cracked gas to below the water dew point, so that water condenses and ammonia is washed out of the cracked gas by the condensed water. If the cracked gas is cooled to temperatures between 30°C and 70°C, the amount of water fed into the cracking tubes together with the ammonia as a temperature moderator is sufficient to reduce the ammonia content to such an extent that the part of the ammonia remaining in the cracked gas can be removed without economic Disadvantages can be separated by the pressure swing adsorption. A separate supply of washing water is not necessary, at least in normal operation.
Vorzugsweise wird das in der Wasserwäsche erhaltene Ammoniak/Wasser-Gemisch wieder im Spaltofen eingesetzt, wobei der größte Teil des Gemisches zur Wasserstoffgewinnung in die Spaltrohre geführt und der restliche Teil zur Einstellung der in die Spaltrohre eigebrachten Wassermenge geregelt ausgeschleust und beispielsweise zur Befeuerung des Spaltofens verwendet wird. The ammonia/water mixture obtained in the water wash is preferably reused in the cracking furnace, with most of the mixture being fed into the cracking tubes to produce hydrogen and the remaining part being discharged in a controlled manner to adjust the amount of water introduced into the cracking tubes and used, for example, to fire the cracking furnace will.
Bei dieser Verfahrensweise kann es Vorkommen, dass während des Anfahrbetriebs nicht genügend Wasser zum Spaltofen zurückgeführt wird, um den Ammoniakgehalt des Spaltgases durch Wäsche mit auskondensiertem Wasser ausreichend weit zu reduzieren. Für diesen Fall ist erfindungsgemäß vorgesehen, der Wasserwäsche zusätzlich Wasser von außen zuzuführen. With this procedure, it can happen that not enough water is fed back to the cracking furnace during the start-up operation in order to sufficiently reduce the ammonia content of the cracked gas by scrubbing with condensed water. In this case, the invention provides for water to be additionally supplied to the water wash from the outside.
Zur Vermeidung einer Überhitzung des Spaltofens während des Abfahrbetriebs ist vorgesehen, die Spaltrohre mit Dampf oder Stickstoff zu kühlen. To prevent the cracking furnace from overheating during shutdown, the cracking tubes will be cooled with steam or nitrogen.
Um die im Verfahren eingesetzte Energie effektiver nutzen zu können, sieht eine Ausgestaltung des erfindungsgemäßen Verfahrens vor, das im Spaltofen erhaltene heiße Spaltgas zur Beheizung eines Spaltreaktors zu nutzen, in dem durch die Spaltung von Ammoniak in Wasserstoff und Stickstoff ein weiters Spaltgas gebildet wird. Das im Spaltreaktor aus einem Teil oder der Gesamtmenge des Ammoniak enthaltenden Einsatzstoffs gebildete Spaltgas wird entweder in den Spaltrohren des Spaltofens weiterbehandelt oder mit dem bei der Beheizung des Spaltreaktors abgekühlten Spaltgas zusammengeführt.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Erzeugung eines Wasserstoffprodukts aus Ammoniak, mit einem zumindest einen Brenner umfassenden Spaltofen zur katalytisch unterstützten Umsetzung eines Ammoniak enthaltenden Einsatzstoffs zu einem Wasserstoff und Stickstoff enthaltenden Spaltgas, einer Trenneinrichtung, mit der Wasserstoff aus dem Spaltgas unter Erhalt eines stickstoffreichen, brennbare Stoffe umfassenden Restgases abgetrennt werden kann, sowie einer Rückführeinrichtung, über die zumindest ein Teil des Restgases zurückführbar ist, um über den zumindest einen Brenner zur Befeuerung des Spaltofens verbrannt zu werden. In order to be able to use the energy used in the process more effectively, one embodiment of the process according to the invention provides for the hot cracked gas obtained in the cracking furnace to be used to heat a cracking reactor in which a further cracked gas is formed by cracking ammonia into hydrogen and nitrogen. The cracked gas formed in the cracking reactor from part or all of the ammonia-containing feedstock is either further treated in the cracking tubes of the cracking furnace or combined with the cracked gas cooled during heating of the cracking reactor. Furthermore, the invention relates to a device for producing a hydrogen product from ammonia, with a cracking furnace comprising at least one burner for the catalytically supported conversion of an ammonia-containing feedstock into a cracked gas containing hydrogen and nitrogen, a separating device with which hydrogen is separated from the cracked gas while obtaining a nitrogen-rich, combustible substances can be separated comprehensive residual gas, as well as a recirculation device, through which at least part of the residual gas can be returned to be burned over the at least one burner for firing the cracking furnace.
Vorrichtungsseitig wird die gestellte Aufgabe erfindungsgemäß dadurch gelöst, dass die Vorrichtung eine mit dem zumindest einen Brenner verbundene Sauerstoffquelle umfasst, aus der ein sauerstoffreicher Stoffstrom entnommen und direkt oder nach Zumischung von Luft bei der Verbrennung des Restgases als Oxidationsmittel eingesetzt werden kann. On the device side, the stated object is achieved according to the invention in that the device comprises an oxygen source connected to the at least one burner, from which an oxygen-rich material flow can be taken and used as an oxidizing agent directly or after the admixture of air in the combustion of the residual gas.
Vorzugsweise handelt es sich bei der Sauerstoffquelle um einen Elektrolyseur, der Wasser elektrochemisch zerlegen und einen Wasserstoff- sowie einen sauerstoffreichen Stoffstrom erzeugen kann. Der Elektrolyseur kann eine Festoxid- Elektrolysezelle umfassen, die bei Betriebstemperaturen zwischen 500°C und 850°C Wasserdampf spalten und einen heißen sauerstoffreichen Stoffstrom erzeugen kann. Preferably, the source of oxygen is an electrolyzer capable of electrochemically breaking down water and producing a stream of hydrogen and an oxygen-rich stream. The electrolyser may comprise a solid oxide electrolytic cell capable of splitting water vapor at operating temperatures between 500°C and 850°C and producing a hot, oxygen-rich stream of material.
Die Trenneinrichtung umfasst bevorzugt einen Druckwechseladsorber, der in der Lage ist, aus dem Spaltgas eine aufgrund ihrer Reinheit und ihres Ducks als Produkt abgebbare Wasserstofffraktion abzutrennen und über eine Produktgasleitung einem Abnehmer zuzuführen. Stickstoff sowie ebenfalls im Spaltgas vorliegendes Ammoniak können dem Druckwechseladsorber als Restgas entnommen werden. The separating device preferably comprises a pressure swing adsorber which is able to separate from the cracked gas a hydrogen fraction which can be released as a product due to its purity and pressure and to feed it to a consumer via a product gas line. Nitrogen and also ammonia present in the cracked gas can be removed from the pressure swing adsorber as residual gas.
Zweckmäßigerweise ist der als Sauerstoffquelle dienende Elektrolyseur nicht nur mit dem zumindest einen Brenner des Spaltofens, sondern auch mit der Trenneinrichtung verbunden, so dass der durch den Elektrolyseur erzeugbare wasserstoffreiche Stoffstrom dazu verwendet werden kann, die Menge der durch die Ammoniakspaltung erzeugten, als Produkt angebbaren Wasserstofffraktion zu ergänzen. Falls die Zusammensetzung des wasserstoffreichen Stoffstroms nicht den an ein Wasserstoffprodukt gestellten Anforderungen genügt, kann zur Abtrennung von
Verunreinigungen zwischen dem Elektrolyseur und der Trenneinrichtung eine Reinigungsvorrichtung angeordnet sein. Alternativ kann der Elektrolyseur mit der Trenneinrichtung stromaufwärts des Druckwechseladsorbers verbunden sein, so dass im wasserstoffreichen Stoffstrom enthaltene Verunreinigungen durch den Druckwechseladsorber entfernt werden können. The electrolyser serving as the oxygen source is expediently connected not only to the at least one burner of the cracking furnace, but also to the separating device, so that the hydrogen-rich material flow that can be generated by the electrolyser can be used to reduce the quantity of the hydrogen fraction that is generated by the ammonia cracking and can be specified as a product to complete. If the composition of the hydrogen-rich stream does not meet the requirements placed on a hydrogen product, the separation of Impurities between the electrolyzer and the separator may be arranged a cleaning device. Alternatively, the electrolyzer can be connected to the separating device upstream of the pressure swing adsorber, so that impurities contained in the hydrogen-rich substance stream can be removed by the pressure swing adsorber.
Solange der Ammoniakgehalt einen Grenzwert nicht überschreitet, kann die Abtrennung von Stickstoff und Ammoniak aus dem Spaltgas wirtschaftlich mit Hilfe eines Druckwechseladsorbers durchgeführt werden. Sinnvollerweise wird dann das Spaltgas stromaufwärts des Druckwechseladsorbers nicht bis zum Taupunkt abgekühlt, um einen Eintrag von Flüssigkeit in den Druckwechseladsorber zu verhindern. Hierzu kann die erfindungsgemäße Vorrichtung beispielsweise mit einem regelbaren Luftkühler zur kontrollierten Spaltgaskühlung ausgeführt sein. Falls der Ammoniakgehalt des Spaltgases über dem Grenzwert liegt, wird vorgeschlagen, stromaufwärts des Druckwechseladsorbers eine Wasserwäsche anzuordnen, die sinnvollerweise in der Lage ist, Ammoniak auszuwaschen und den Ammoniakgehalt des Spaltgases unter Bildung eines Ammoniak/Wasser-Gemisches bis unter den Grenzwert abzusenken. Weiterhin wird vorgeschlagen, die Wasserwäsche mit dem Spaltofen so zu verbinden, dass zumindest ein Teil des Ammoniak/Wasser-Gemisches in die Spaltrohre zurückgeführt werden kann. As long as the ammonia content does not exceed a limit value, the separation of nitrogen and ammonia from the cracked gas can be carried out economically using a pressure swing adsorber. It makes sense then that the cracked gas upstream of the pressure swing adsorber is not cooled down to the dew point in order to prevent liquid from entering the pressure swing adsorber. For this purpose, the device according to the invention can be designed, for example, with an adjustable air cooler for controlled cracked gas cooling. If the ammonia content of the cracked gas is above the limit value, it is proposed to arrange a water scrubber upstream of the pressure swing adsorber, which is sensibly capable of washing out ammonia and reducing the ammonia content of the cracked gas to below the limit value, forming an ammonia/water mixture. Furthermore, it is proposed to connect the water wash with the cracking furnace in such a way that at least part of the ammonia/water mixture can be fed back into the cracking tubes.
Bevorzugt ist die Wasserwäsche mit einer Kühleirichtung ausgeführt, über die das Spaltgas bis unterhalb des Wassertaupunkts abkühlbar ist, so dass Wasser kondensieren und Ammoniak durch das kondensierte Wasser aus dem Spaltgas ausgewaschen werden kann. Besonders bevorzugt ist die Wasserwäsche ohne eine Zuführeinrichtung für zusätzliches Waschwasser und einer Kühleinrichtung ausgeführt, die in der Lage ist, das Spaltgas bis auf Temperaturen zwischen 30°C und 70°C abzukühlen. The water scrubbing is preferably carried out with a cooling device, via which the cracked gas can be cooled to below the water dew point, so that water can condense and ammonia can be washed out of the cracked gas by the condensed water. The water scrubbing is particularly preferably carried out without a supply device for additional scrubbing water and a cooling device which is able to cool the cracked gas down to temperatures between 30.degree. C. and 70.degree.
Die erfindungsgemäße Vorrichtung kann einen mit dem Spaltofen verbunden Spaltreaktor zur Spaltung von Ammoniak umfassen, der durch heißes, im Spaltofen erhältliche Spaltgas beheizbar ist.
Im Folgenden soll die Erfindung anhand eines in der Figur 1 schematisch dargestellten Ausführungsbeispiels näher erläutert werden. The device according to the invention can comprise a cracking reactor connected to the cracking furnace for cracking ammonia, which can be heated by hot cracking gas available in the cracking furnace. The invention will be explained in more detail below with reference to an exemplary embodiment shown schematically in FIG.
Die Figur 1 zeigt die Erzeugung von Wasserstoff aus Ammoniak gemäß einer bevorzugten Ausgestaltung der Erfindung, bei der ein Elektrolyseur mit einer Festoxid- Elektrolysezelle als Sauerstoffquelle dient. FIG. 1 shows the production of hydrogen from ammonia according to a preferred embodiment of the invention, in which an electrolyzer with a solid oxide electrolytic cell serves as the oxygen source.
Über Leitung 1 wird dem Spaltofen S ein weitgehend aus Ammoniak bestehender, Wasser enthaltender Einsatzstoff zugeführt und in die Spaltrohre R eingeleitet, die mit durch den Brenner B erzeugter Wärme 2 beheizt werden. Mit katalytischerAn input material consisting largely of ammonia and containing water is fed to the cracking furnace S via line 1 and introduced into the cracking tubes R, which are heated with heat 2 generated by the burner B. With catalytic
Unterstützung wird bei Temperaturen zwischen 500 und 1000°C der überwiegende Teil des zugeführten Ammoniaks gespalten, so dass den Spaltrohren R ein heißes, weitgehend aus Stickstoff und Wasserstoff bestehendes, Wasser und nicht umgesetztes Ammoniak enthaltendes Spaltgas 3 entnommen und in die Trenneinrichtung T überführt werden kann. In der zur Trenneinrichtung T gehörenden Wasserwäsche Wwird das Spaltgas 3 auf Temperaturen zwischen 30°C und 70°C abgekühlt, wobei Wasser auskondensiert und einen Großteil des Ammoniaks auswäscht. Während das dabei gebildete Ammoniak/Wasser-Gemisch 4 zur Erhöhung der Wasserstoffausbeute des Verfahrens in die Spaltrohre R zurückgeführt wird, wird das weitgehend wasser- und ammoniakfreie Spaltgas 5 in den Druckwechseladsorber D geleitet, wo es in eine Produktreinheit aufweisende Wasserstofffraktion 6 und ein Restgas 7 getrennt wird. Das Restgas 7, das zum überwiegenden Teil aus Stickstoff besteht, daneben aber auch brennbare Komponenten wie Ammoniak und Wasserstoff enthält, wird dem Brenner B als Brennstoff zugeführt und gemeinsam mit dem Oxidationsmittel 8 verbrannt. Die Restwärme der gegen die Spaltrohre R abgekühlten Rauchgase 15 des Brenners B wird in einem Abhitzesystem (nicht dargestellt) beispielsweise zur Verdampfung und Vorwärmung des Einsatzstoffs 1 verwendet. With support, the majority of the ammonia supplied is cracked at temperatures between 500 and 1000° C., so that a hot cracked gas 3, consisting largely of nitrogen and hydrogen, containing water and unreacted ammonia, can be removed from the cracking tubes R and transferred to the separating device T . In the water wash W belonging to the separating device T, the cracked gas 3 is cooled to temperatures between 30° C. and 70° C., with water condensing out and washing out a large part of the ammonia. While the ammonia/water mixture 4 formed in the process is fed back into the cracking tubes R to increase the hydrogen yield of the process, the cracked gas 5, which is largely free of water and ammonia, is fed into the pressure swing adsorber D, where it is divided into a product-pure hydrogen fraction 6 and a residual gas 7 is separated. The residual gas 7 , which mainly consists of nitrogen but also contains combustible components such as ammonia and hydrogen, is fed to the burner B as fuel and burned together with the oxidizing agent 8 . The residual heat of the flue gases 15 of the burner B, which have been cooled against the cracking tubes R, is used in a waste heat system (not shown), for example for evaporating and preheating the feedstock 1 .
Das Oxidationsmittel 8, das einen höheren Sauerstoffgehalt als Luft aufweist, wird dem als Sauerstoffquelle fungierenden Elektrolyseurs E entnommen. Der eine Festoxid- Elektrolysezelle umfassende Elektrolyseur E spaltet bei Betriebstemperaturen zwischen 500°C und 950°C Wasserdampf. In der Elektrolysezelle trennt ein aus einem für Sauerstoffionen leitfähigen Material bestehender Elektrolyt M einen Kathoden- K von einem Anodenraum A. Der in den Kathodenraum K eingebrachte Wasserdampf 9 wird an der Grenzfläche zum Elektrolyten M in Wasserstoff, der auf der Kathodenseite
verbleibt, und Sauerstoffionen gespalten, die zur Anodenseite wandern, wo sie zu Sauerstoffmolekülen oxidiert werden. Der Anodenraum A wird mit Luft 10 gespült wobei das heiße Oxidationsmittel 8 entsteht, das ohne Kühlung dem Brenner B zugeführt wird. Aus dem Kathodenraum K wird ein wasserstoffreicher Stoffstrom 11 abgezogen und mit der Produktreinheit aufweisende Wasserstofffraktion 6 zumThe oxidizing agent 8, which has a higher oxygen content than air, is taken out from the electrolyzer E functioning as an oxygen source. The electrolyser E, which includes a solid oxide electrolytic cell, splits water vapor at operating temperatures between 500°C and 950°C. In the electrolytic cell, an electrolyte M consisting of a material that is conductive for oxygen ions separates a cathode K from an anode compartment A remains, and oxygen ions are split, which migrate to the anode side, where they are oxidized to oxygen molecules. The anode chamber A is flushed with air 10, the hot oxidizing agent 8 being produced, which is fed to the burner B without cooling. From the cathode compartment K, a hydrogen-rich stream 11 is withdrawn and with the product purity having hydrogen fraction 6 to
Wasserstoffprodukt 12 gemischt. Optional können dem Brenner B Luft 13 als weiters Oxidationsmittel und/oder Ammoniak 14 als Zusatzbrennstoff zugeführt werden.
Hydrogen product 12 mixed. Optionally, the burner B can be supplied with air 13 as a further oxidizing agent and/or ammonia 14 as an additional fuel.
Claims
1. Verfahren zur Erzeugung eines Wasserstoffprodukts (6) aus Ammoniak, wobei ein Ammoniak enthaltender Einsatzstoff (1) unter Verwendung eines brennerbefeuerten Spaltofens (S) mit katalytischer Unterstützung zu einem Wasserstoff und Stickstoff enthaltenden Spaltgas (3) umgesetzt wird, von dem das1. A process for producing a hydrogen product (6) from ammonia, in which an ammonia-containing feedstock (1) is converted using a burner-fired cracking furnace (S) with catalytic support to form a cracked gas (3) containing hydrogen and nitrogen, from which the
Wasserstoffprodukt (6) unter Erhalt eines stickstoffreichen, brennbare Stoffe umfassenden Restgases (7) abgetrennt wird, wobei zumindest ein Teil des Restgases (7) zur Befeuerung des Spaltofens (S) verbrannt wird, dadurch gekennzeichnet, dass aus einer Sauerstoffquelle (E) ein sauerstoffreicher Stoffstrom (8) zugeführt und direkt oder nach Zumischung von Luft (13) bei derHydrogen product (6) is separated to obtain a nitrogen-rich residual gas (7) comprising combustible substances, at least part of the residual gas (7) being burned to fire the cracking furnace (S), characterized in that an oxygen-rich source (E) is converted into an oxygen-rich Material flow (8) fed and directly or after the admixture of air (13) at the
Verbrennung des Restgases (7) als Oxidationsmittel eingesetzt wird. Combustion of the residual gas (7) is used as an oxidizing agent.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als Sauerstoffquelle ein Elektrolyseur (E) genutzt wird, in dem durch elektrochemische Zerlegung von Wasser (9) ein Wasserstoff- (11) sowie ein sauerstoffreicher Stoffstrom (8) gewonnen werden. 2. The method according to claim 1, characterized in that an electrolyzer (E) is used as the oxygen source, in which a hydrogen (11) and an oxygen-rich stream (8) are obtained by electrochemical decomposition of water (9).
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass der Elektrolyseur (E) eine anodenseitig mit Luft (10) gespülte Festoxid-Elektrolysezelle umfasst und die bei der Spülung angewärmte und mit Sauerstoff angereicherte Luft als Oxidationsmittel (8) zur Verbrennung des Restgases (7) eingesetzt wird. 3. The method according to claim 2, characterized in that the electrolyser (E) comprises a solid oxide electrolytic cell flushed with air (10) on the anode side and the air heated during flushing and enriched with oxygen is used as an oxidizing agent (8) for burning the residual gas (7 ) is used.
4. Verfahren nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, dass der im Elektrolyseur (E) gewonnene wasserstoffreiche Stoffstrom (11) als Brennstoff zur Befeuerung des Spaltofens (S) und/oder zur Ergänzung der Menge des durch die Ammoniakspaltung erzeugten Wasserstoffs (6) verwendet werden. 4. The method according to any one of claims 2 or 3, characterized in that in the electrolyzer (E) obtained hydrogen-rich stream (11) as fuel for firing the cracking furnace (S) and / or to supplement the amount of hydrogen produced by the ammonia cracking ( 6) are used.
5. Verfahren nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass zur Trennung des Spaltgases (5) ein Druckwechseladsorber (D) eingesetzt wird.5. The method according to any one of claims 2 to 4, characterized in that a pressure swing adsorber (D) is used to separate the cracked gas (5).
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das im Spaltgas (3) zur Entfernung vom im Spaltofen (S) nicht umgesetzten Ammoniaks einer Wasserwäsche (W) unterzogen wird. 6. The method according to any one of claims 1 to 5, characterized in that in the cracking gas (3) to remove the in the cracking furnace (S) unreacted ammonia is subjected to a water wash (W).
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das Spaltgas (5) in der Wasserwäsche (W) auf eine Temperatur zwischen 30 und 70°C abgekühlt wird,
um Wasser auszukondensieren und Ammoniak durch das auskondensierte Wasser auszuwaschen. 7. The method according to claim 6, characterized in that the cracked gas (5) in the water wash (W) is cooled to a temperature between 30 and 70 ° C, to condense water and wash out ammonia by the condensed water.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass aus dem Spaltgas (5) in der Wasserwäschen (W) ausgewaschenes Ammoniak (4) in den Spaltofen (S) zurückgeführt wird. 8. The method according to any one of claims 1 to 7, characterized in that from the cracked gas (5) in the water scrubber (W) washed ammonia (4) is returned to the cracking furnace (S).
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass im Spaltofen erhaltenes heißes Spaltgas zur Beheizung eines Spaltreaktors genutzt wird, in dem durch die Spaltung von Ammoniak in Wasserstoff und Stickstoff ein weiters Spaltgas gebildet wird. 9. The method according to any one of claims 1 to 8, characterized in that obtained in the cracking furnace hot cracked gas is used to heat a cracking reactor in which a further cracked gas is formed by the cracking of ammonia into hydrogen and nitrogen.
10. Vorrichtung zur Erzeugung eines Wasserstoffprodukts (6) aus Ammoniak, mit einem zumindest einen Brenner (B) umfassenden Spaltofen (S) zur katalytisch unterstützten Umsetzung eines Ammoniak enthaltenden Einsatzstoffs (1) zu einem Wasserstoff und Stickstoff enthaltenden Spaltgas (3), einer Trenneinrichtung (T), mit der Wasserstoff (6) aus dem Spaltgas (3) unter Erhalt eines stickstoffreichen, brennbare Stoffe umfassenden Restgases (7) abgetrennt werden kann, sowie einer Rückführeinrichtung, über die zumindest ein Teil des Restgases (7) zurückführbar ist, um über den zumindest einen Brenner (B) zur Befeuerung des Spaltofens (S) verbrannt zu werden, dadurch gekennzeichnet, dass sie eine mit dem zumindest einen Brenner (B) verbundene Sauerstoffquelle (E) umfasst, aus der ein sauerstoffreicher Stoffstrom (8) entnommen und direkt oder nach10. Device for producing a hydrogen product (6) from ammonia, with a cracking furnace (S) comprising at least one burner (B) for the catalytically supported conversion of an ammonia-containing feedstock (1) into a cracked gas (3) containing hydrogen and nitrogen, a separating device (T), with which the hydrogen (6) can be separated from the cracked gas (3) to obtain a nitrogen-rich residual gas (7) containing combustible substances, and a recirculation device via which at least part of the residual gas (7) can be recycled in order to to be burned via the at least one burner (B) for firing the cracking furnace (S), characterized in that it comprises an oxygen source (E) connected to the at least one burner (B), from which an oxygen-rich material stream (8) is removed and directly or after
Zumischung von Luft (13) bei der Verbrennung des Restgases (7) als Oxidationsmittel eingesetzt werden kann. Admixture of air (13) in the combustion of the residual gas (7) can be used as an oxidizing agent.
11. Vorrichtung nach Anspruch 10, dadurch gekennzeichnet, dass es sich bei der Sauerstoffquelle um einen Elektrolyseur (E) handelt, der Wasser (9) elektrochemisch zerlegen und einen Wasserstoff- (11) sowie einen sauerstoffreichen Stoffstrom (8) erzeugen kann. 11. The device according to claim 10, characterized in that the oxygen source is an electrolyser (E) which electrochemically decomposes water (9) and can generate a hydrogen (11) and an oxygen-rich substance stream (8).
12. Vorrichtung nach einem der Ansprüche 10 oder 11, dadurch gekennzeichnet, dass die Trenneinrichtung (T) einen Druckwechseladsorber (D) umfasst. 12. Device according to one of claims 10 or 11, characterized in that the separating device (T) comprises a pressure swing adsorber (D).
13. Vorrichtung nach Anspruch 12, dadurch gekennzeichnet, dass die Trenneinrichtung (T) eine stromaufwärts des Druckwechseladsorbers (D) angeordnet Wasserwäsche (W) zur Abtrennung von Ammoniak (4) aus dem Spaltgas (3) umfasst.
13. Device according to claim 12, characterized in that the separating device (T) comprises a water scrubber (W) arranged upstream of the pressure swing adsorber (D) for separating ammonia (4) from the cracked gas (3).
14. Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, dass die Wasserwäsche (W) ohne eine Zuführeinrichtung für zusätzliches Waschwasser und einer Kühleinrichtung ausgeführt, die in der Lage ist, das Spaltgas (3) bis auf Temperaturen zwischen 30°C und 70°C abzukühlen. 14. Device according to claim 13, characterized in that the water wash (W) is carried out without a supply device for additional wash water and a cooling device which is able to cool the cracked gas (3) down to temperatures between 30°C and 70°C .
15. Vorrichtung nach einem der Ansprüche 10 bis 14, dadurch gekennzeichnet, dass sie einen Spaltreaktor zur Spaltung von Ammoniak umfasst, der durch im Spaltofen (S) erhältliches Spaltgas beheizbar ist.
15. Device according to one of claims 10 to 14, characterized in that it comprises a cleavage reactor for the cleavage of ammonia, which can be heated by cleavage gas available in the cleavage furnace (S).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21020333.7A EP4112539A1 (en) | 2021-06-30 | 2021-06-30 | Method and device for producing hydrogen from ammonia |
| PCT/EP2022/025255 WO2023274572A1 (en) | 2021-06-30 | 2022-06-01 | Method and device for producing hydrogen from ammonia |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4363371A1 true EP4363371A1 (en) | 2024-05-08 |
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ID=76744580
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21020333.7A Withdrawn EP4112539A1 (en) | 2021-06-30 | 2021-06-30 | Method and device for producing hydrogen from ammonia |
| EP22731483.8A Pending EP4363371A1 (en) | 2021-06-30 | 2022-06-01 | Method and device for producing hydrogen from ammonia |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
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| EP21020333.7A Withdrawn EP4112539A1 (en) | 2021-06-30 | 2021-06-30 | Method and device for producing hydrogen from ammonia |
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| EP (2) | EP4112539A1 (en) |
| KR (1) | KR20240026451A (en) |
| WO (1) | WO2023274572A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040163313A1 (en) * | 2003-02-20 | 2004-08-26 | Buxbaum Robert E. | Hydrogen generation apparatus |
| US20130177489A1 (en) * | 2012-01-05 | 2013-07-11 | Alstom Technology Ltd | Carbon dioxide removal system with a membrane separator system for ammonia recovery |
| US10112829B2 (en) * | 2016-01-19 | 2018-10-30 | Fluor Technologies Corporation | Production of pure hydrogen from ammonia rich sour water stripper overhead |
| CN206846710U (en) * | 2017-05-19 | 2018-01-05 | 希格茨曼（天津）控制系统工程有限公司 | A kind of oxygen-enriched energy-saving burner of ammonia destruction furnace |
| KR102587486B1 (en) * | 2017-08-07 | 2023-10-11 | 가스 테크놀로지 인스티튜트 | Apparatus and method for producing hydrogen through ammonia decomposition |
| CN110205637A (en) * | 2019-07-03 | 2019-09-06 | 浙江工业大学 | A kind of amino solar heat chemical solids oxide electrolysis water hydrogen generating system |
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2021
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- 2022-06-01 EP EP22731483.8A patent/EP4363371A1/en active Pending
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