EP4253572A1 - Réduction à base d'ammoniac nh3 de matériau contenant de l'oxyde métallique - Google Patents
Réduction à base d'ammoniac nh3 de matériau contenant de l'oxyde métallique Download PDFInfo
- Publication number
- EP4253572A1 EP4253572A1 EP22194331.9A EP22194331A EP4253572A1 EP 4253572 A1 EP4253572 A1 EP 4253572A1 EP 22194331 A EP22194331 A EP 22194331A EP 4253572 A1 EP4253572 A1 EP 4253572A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- ammonia
- reducing
- reduction reactor
- top gas
- 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
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- 230000009467 reduction Effects 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 50
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 43
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 221
- 230000001603 reducing effect Effects 0.000 claims abstract description 147
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 108
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims description 304
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 104
- 239000001257 hydrogen Substances 0.000 claims description 70
- 229910052739 hydrogen Inorganic materials 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 58
- 229910052757 nitrogen Inorganic materials 0.000 claims description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 49
- 239000003345 natural gas Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- -1 N2 Natural products 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 37
- 150000002431 hydrogen Chemical class 0.000 description 35
- 238000010438 heat treatment Methods 0.000 description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 238000003776 cleavage reaction Methods 0.000 description 10
- 238000011946 reduction process Methods 0.000 description 10
- 230000007017 scission Effects 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 235000013980 iron oxide Nutrition 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 239000010981 turquoise Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
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- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/06—Making pig-iron in the blast furnace using top gas in the blast furnace process
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/26—Increasing the gas reduction potential of recycled exhaust gases by adding additional fuel in recirculation pipes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
- C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
- C21B2100/284—Increasing the gas reduction potential of recycled exhaust gases by separation of nitrogen
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/80—Interaction of exhaust gases produced during the manufacture of iron or steel with other processes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2300/00—Process aspects
- C21B2300/04—Modeling of the process, e.g. for control purposes; CII
Definitions
- the application relates to a method and device for the reduction of metal oxide-containing material, wherein reducing gas obtained using ammonia NH 3 is used.
- Hydrogen can be used as the only reducing gas, or in combination with other gases, for example natural gas-based reducing gases.
- ammonia offers significant advantages over hydrogen H 2 in terms of storage and transport.
- Ammonia can be split into nitrogen and hydrogen 2NH3 ⁇ N2 + 3H2 .
- Hydrogen H 2 can react as a reducing agent with metal oxides, for example iron oxides: 3 Fe 2 O 3 + H 2 ⁇ 2 Fe 3 O 4 + H 2 O Fe 3 O 4 + H 2 ⁇ 3 FeO + H 2 O FeO + H 2 ⁇ Fe + H 2 O.
- metal oxides for example iron oxides: 3 Fe 2 O 3 + H 2 ⁇ 2 Fe 3 O 4 + H 2 O Fe 3 O 4 + H 2 ⁇ 3 FeO + H 2 O FeO + H 2 ⁇ Fe + H 2 O.
- ammonia can also act as a reducing agent itself: 9 Fe 2 O 3 + 2 NH 3 ⁇ 6 Fe 3 O 4 + N 2 + 3 H 2 O 3 Fe 3 O 4 + 2 NH 3 ⁇ 9 FeO + N 2 + 3 H 2 O 3 FeO + 2 NH 3 ⁇ 3 Fe + N 2 + 3 H 2 O.
- reducing gas obtained using ammonia NH 3 can be used to reduce material containing metal oxide;
- a reducing gas can be, for example, ammonia NH 3 , or a mixture of ammonia NH 3 with one or more other gases - preferably one or more of which can have a reducing effect on metal oxide-containing material - which, for example, is the case with a mixture of ammonia and its cleavage products, hydrogen H 2 and nitrogen N 2 would be the case, although of course other gases could also be contained in the mixture.
- reducing gas obtained using ammonia NH 3 can also be a reducing gas act, which does not contain ammonia NH 3 , but the cleavage product obtained from a cleavage contains hydrogen H 2 - alone or together with the cleavage product nitrogen N 2 -, optionally in a mixture with one or more other gases - preferably one or more metal oxide-containing material can have a reducing effect.
- the material containing metal oxide is preferably a material containing iron oxide.
- the reduction process is, for example, a direct reduction process.
- the reducing gas is obtained using ammonia NH 3 .
- Such a reducing gas can be, for example, ammonia NH 3 , or a mixture of ammonia NH 3 with one or more other gases - preferably one or more of which can have a reducing effect on metal oxide-containing material - which, for example, is the case with a mixture of ammonia and its cleavage products, hydrogen H 2 and nitrogen N 2 would be the case, although of course other gases could also be contained in the mixture.
- a reducing gas can be, for example, ammonia NH 3 , or a mixture of ammonia NH 3 with one or more other gases - preferably one or more of which can have a reducing effect on metal oxide-containing material - which, for example, is the case with a mixture of ammonia and its cleavage products, hydrogen H 2 and nitrogen N 2 would be the case, although of course other gases could also be contained in the mixture.
- the reducing gas obtained using ammonia NH 3 can also be a reducing gas that does not contain ammonia NH 3 , but the cleavage product obtained from a cleavage contains hydrogen H 2 - alone or together with the cleavage product nitrogen N 2 -, if necessary in a mixture with one or more other gases - preferably one or more being able to have a reducing effect on metal oxide-containing material.
- the reducing gas can therefore include ammonia; it can consist partly or completely of ammonia.
- ammonia contains other components;
- One aspect of using the ammonia is mixing it with the other components;
- ammonia can be added to the other components in such a way that it accounts for more than 0.5% by volume of the gas stream obtained after it has been added.
- Other possible components include those which are inert with respect to reactions with the metal oxide-containing material under the conditions prevailing in the reduction reactor - for example nitrogen N 2 - and those which react with the metal oxide-containing material under the conditions prevailing in the reduction reactor.
- components that have a reducing effect on the metal oxide-containing material are preferred; it can be, for example, hydrocarbon-containing gases, carbon-containing gases, hydrogen-containing gases, hydrogen.
- Reducing gas can also be obtained using ammonia by splitting ammonia and mixing the resulting gas mixture of nitrogen and hydrogen - optionally after enrichment or depletion of nitrogen or hydrogen - with other components of the reducing gas.
- Reducing gas can also be obtained using ammonia by splitting ammonia and mixing the resulting hydrogen with other components of the reducing gas after separation from the nitrogen, or the entire reducing gas - if necessary with remaining small amounts of nitrogen formed during the splitting - provides.
- ammonia of any “color” is suitable.
- Cold means the coloring in connection with the underlying type of production.
- the color of ammonia is often linked to the color of the hydrogen used in production.
- the ammonia can, for example, be green, for example if it was produced using green hydrogen; it can be blue, for example if it was produced using hydrogen obtained by sequestering the resulting carbon dioxide CO 2 .
- the ammonia can also be produced using turquoise hydrogen, for example if the hydrogen is under Deposition of resulting carbon C is generated; it can be produced using pink hydrogen, for example if the hydrogen is produced using nuclear power.
- the reducing gas is the gas introduced into the reduction reactor or its interior containing metal oxide-containing material - in which the reduction reactions take place - with its composition and temperature at the time of introduction.
- a precursor of the reducing gas is present, on the basis of which the reducing gas is prepared.
- the preparation can be carried out, for example, by adding further components or heating.
- the preparation can also be carried out by chemical reactions taking place in the precursor without external intervention, which, for example, change the chemical composition or the temperature.
- the reduction reactor is, for example, a reduction shaft - for example when carrying out a direct reduction process with a reduction shaft containing a fixed bed of material containing metal oxide.
- the reduction reactor is, for example, a fluidized bed reactor - for example when carrying out a direct reduction process with a reduction reactor containing a fluidized bed of material containing metal oxide.
- the fluidized bed reactor can also include several individual partial reactors, which are connected, for example, in parallel or sequentially and together form the fluidized bed reactor.
- the reduction reactor is, for example, a fluidized bed reactor - for example when carrying out a direct reduction process with a fluidized bed containing material containing metal oxide Reduction reactor.
- the fluidized bed reactor can also include several individual partial reactors, which are connected, for example, in parallel or sequentially and together form the fluidized bed reactor.
- the reduction reactor can also be a blast furnace that contains a fixed bed comprising metal oxide-containing material - when operating a blast furnace, ammonia can, for example, replace PCI coal or fossil reducing gases.
- a top gas is discharged from the reduction reactor.
- the top gas is created from the reducing gas as it flows through the reduction reactor due to the reactions of its components with the metal oxide-containing material or the products resulting from these reactions, for example the resulting metallic iron, which take place in the reduction reactor.
- the top gas has less reducing power than the reducing gas.
- At least a portion of the top gas is used - if necessary after processing - as a component in the preparation of the reducing gas.
- Use of a subset occurs both when, with the composition of the top gas unchanged, only a subset of the resulting top gas volume is used, and when not all components of the resulting top gas are used - for example, when an enrichment of a component - for example enrichment of hydrogen - takes place and the correspondingly enriched gas stream is used completely or partially.
- One step in the preparation of the reducing gas is - if no preparation takes place - the mixing of top gas with other components of the reducing gas; Either the resulting gas mixture forms the reducing gas, or the reducing gas is prepared on the basis of this gas mixture, with further steps such as adding additional components or heating to the gas mixture desired temperature when introduced into the reduction reactor, or chemical reactions leading to a change in the composition take place.
- the top gas is subjected to processing.
- Dedusting is preferably carried out dry, as the heat content of the gas can then be used better in the process than with wet dedusting.
- the heat can be used to evaporate the ammonia.
- the heat can also be used elsewhere in the process, possibly via a heat transfer medium, for example to generate hot water and/or steam.
- water vapor content is advantageous, for example, if natural gas is reformed with steam in a reformer when preparing reducing gas. This is also why the water vapor content is set to a desired level advantageous because they relate to the reducing gas quality - expressed as the ratio of the volume percent contents of carbon monoxide CO, hydrogen H 2 , carbon dioxide CO 2 , water H 2 O (CO+H 2 )/(CO 2 +H 2 O) or of Hydrogen H 2 and water H 2 OH 2 /H 2 O - affects.
- processing gas The gas obtained after the processing step or steps is called processing gas in the context of the present application.
- processing gas is used as a component in the preparation of the reducing gas - top gas is then used indirectly via the processing gas obtained on the basis of the top gas in the preparation of the reducing gas.
- One step in the preparation of the reducing gas is then mixing the processing gas with other components of the reducing gas; Either the resulting gas mixture forms the reducing gas, or the reducing gas is prepared on the basis of this gas mixture, with further steps taking place such as adding additional components or heating to the desired temperature when introduced into the reduction reactor, or chemical processes leading to a change in the composition Reactions.
- the top gas has less reducing power than the reducing gas as a result of the reduction reactions that have taken place in the reduction reactor, it still contains components that have a reducing effect - such as hydrogen H 2 - and its reducing power has not yet been exhausted. It also has energy content due to its temperature.
- the energy can be supplied via the reducing gas and can be changed, for example, via the amount and temperature of the reducing gas supplied.
- the reducing gas has a temperature above 750 °C, preferably above 800 °C.
- the specific amount of reducing gas introduced into the reduction reactor is over 2000 Nm 3 /ton of directly reduced iron DRI, preferred is over 2200 Nm 3 /tDRI.
- a lower value is preferred, for example 1500 - 1600 Nm 3 /tDRI.
- top gas - directly as top gas and/or indirectly via processing gas obtained on the basis of the top gas - to prepare the reducing gas enables the use of reduction potential remaining in the top gas and the use of the heat content of the top gas.
- the nitrogen contained in the top gas can be used as a heat transfer medium in the process. Even if the nitrogen is inert with respect to the reduction reactions, it contributes to the resource-saving implementation of the process. Energy that is carried into the reduction reactor by nitrogen via its heat content does not have to be introduced into the reduction reactor by other substances; for example, not from the components of the reducing gas that have a reduction potential.
- This Components - for example ammonia NH 3 , hydrogen H 2 , hydrocarbons - are more expensive and more complex to provide than the nitrogen N 2 that is produced in the splitting of ammonia NH 3 - for every 3 volumes of hydrogen H 2 there is one volume of nitrogen N 2 - and should therefore not necessarily used too hyperstoichiometrically. These components should be used primarily for reduction purposes; Their use without making a significant contribution to the reaction conversion, simply for the input of heat content, is less resource-efficient and time-consuming compared to the use of nitrogen.
- the processing of the top gas withdrawn from the reduction reactor includes a process step for reducing the nitrogen content.
- the top gas is subjected to a treatment which includes at least a reduction in the nitrogen content of the top gas.
- the nitrogen is not completely separated.
- the reduction occurs in order to slow down the enrichment of nitrogen in the reducing gas due to the use of the top gas and the associated reduction in the reducing power of the reducing gas.
- a resulting one Gas stream with increased nitrogen content can be utilized, for example thermally in a reducing gas oven or in a reformer.
- the resulting gas stream with an increased content of reducing components - for example increased hydrogen content - due to the separation of the inert nitrogen - is used in the preparation of the reducing gas.
- the nitrogen content is advantageously reduced in such a way that the reducing gas contains less than 40% by volume, preferably less than 30% by volume, particularly preferably less than 20% by volume of nitrogen.
- the amount of nitrogen contained in the top gas is reduced when the top gas is processed, but the processing gas still contains remaining nitrogen. In this way, the heat content of this nitrogen is used in the process. Even if this nitrogen is inert with regard to the reduction reactions, it contributes to the resource-saving implementation of the process.
- the nitrogen content in the reducing gas can also be controlled and/or regulated to a desired value by appropriately controlling and/or regulating the top gas subset - if necessary after preparation of the top gas - which is not used as a component in the preparation of the reducing gas .
- This subset is removed from the cycle for preparing reducing gas;
- the discharge gas can be used thermally, for example, in a gas oven, reduction gas oven, or reformer. It is preferred if discharge gas is discharged after the top gas has been cooled.
- One or more members of the first group can be added to the top gas and/or the processing gas.
- the ammonia is preferably added in gaseous form.
- the ammonia can be warmed before addition; for example electrically. Heating can be done, for example, by means of a gas oven, whereby the gas oven can be heated, for example, with electrical energy, or by burning fuel.
- the first group is hydrogen obtained from ammonia; so it is ammonia-based hydrogen. This includes the fact that this hydrogen is added as a component of a gas mixture - for example a gas mixture of nitrogen and hydrogen formed during the splitting of ammonia.
- This can be, for example, green, blue, gray, turquoise or pink hydrogen.
- These “colors” mean the coloring in connection with the underlying type of production.
- Green hydrogen is produced, for example, by electrolysis of water using electricity from renewable energies, or by gasification or fermentation of biomass, or steam reforming of biogas - what the types of production of green hydrogen have in common is that the production is CO 2 -free. With blue hydrogen, CO 2 produced during production is stored so that it does not enter the atmosphere; for example, if it was produced by sequestering the resulting carbon dioxide CO 2 . With turquoise hydrogen, C is produced by separating out the resulting carbon. Pink hydrogen involves producing hydrogen using nuclear power. A mixture of one or more of these “colors” of hydrogen is also possible. Gray hydrogen is produced from fossil fuels - for example from natural gas using steam reforming - with the resulting CO 2 predominantly being released into the atmosphere.
- Syngas or synthesis gas refers to industrially produced gas mixtures that mainly contain carbon monoxide and hydrogen in addition to varying amounts of other gases, such as carbon dioxide.
- synthesis gas can be produced from solid, liquid and gaseous starting materials. For example, different crude oil distillates, both low-boiling and high-boiling fractions, can be used as liquid starting materials for synthesis gas.
- the most important gaseous educt for syngas production is natural gas.
- Production methods include steam reforming of natural gas or liquid hydrocarbons, or gasification of coal, biomass or other residues.
- One or more members of the second group can therefore be added to the processing gas.
- Members of the first or second group could also be added to the top gas or the processing gas before the start or completion of the treatment; However, if processing is carried out, it is preferred to add it after the processing has been completed, i.e. to the processing gas.
- the amount of green hydrogen H 2 used can also be increased if the amount of green ammonia NH 3 used is to or must be reduced - for example for reasons of availability or cost.
- At least one member of the second group is added to the resulting gas mixture. That after unification Gas mixture present from top gas or processing gas and at least one member of the first group is a precursor of the reducing gas; At least one member of the second group is added to this precursor.
- the resulting gas mixture can be the reducing gas or a precursor of the reducing gas. If it is a precursor, further steps are carried out such as admixing additional components or heating to the desired temperature when introduced into the reduction reactor or chemical reactions leading to a change in the composition.
- At least one member of the second group is added to the gas mixture created after combining top gas or processing gas and at least one member of the first group
- changes can be made to this gas mixture, such as adding additional components or heating or chemical reactions leading to a change in the composition.
- Heating can be carried out, for example, using electrically operated heating devices.
- Heating can, for example, take place indirectly via gas burners, with one variant also heating the precursor from the resulting exhaust gas via heat exchangers.
- natural gas or top gas can serve as the basis for the fuel for the gas burners; Use of top gas is cheap because its chemical energy is used within the reduction process.
- Chemical reactions that lead to a change in the composition can be initiated, for example, by reforming the precursor - especially when natural gas is added.
- Heating in a reformer used can, for example, take place indirectly via gas burners, with one variant also heating the precursor from the resulting exhaust gas via heat exchangers.
- natural gas or top gas can serve as the basis for the fuel for the gas burners; Use of top gas is cheap because its chemical energy is within the Reduction process is used.
- the resulting gas mixture after combining top gas or processing gas and at least one member of the second group, at least one member of the first group is added to the resulting gas mixture.
- the gas mixture present after the combination of top gas or processing gas and at least one member of the second group is a precursor of the reducing gas; At least one member of the first group is added to this precursor.
- the resulting gas mixture can be the reducing gas or a precursor of the reducing gas. If it is a precursor, further steps are carried out such as admixing additional components or heating to the desired temperature when introduced into the reduction reactor or chemical reactions leading to a change in the composition.
- Heating can, for example, take place indirectly via gas burners, with one variant also heating the precursor from the resulting exhaust gas via heat exchangers.
- natural gas or top gas can serve as the basis for the fuel for the gas burners; Use of top gas is cheap because its chemical energy is used within the reduction process.
- Chemical reactions that lead to a change in the composition can be initiated, for example, by reforming the precursor - especially if natural gas is added.
- Heating in a reformer used can, for example, take place indirectly via gas burners, with one variant also heating the precursor from the resulting exhaust gas via heat exchangers.
- natural gas or top gas can serve as the basis for the fuel for the gas burners.
- Ammonia can be added in top gas, in the processing gas, or in the precursor of the reducing gas.
- ammonia can, for example, be added to the gas that leads to the bustle.
- the ammonia is preferably introduced in gaseous form.
- the ammonia is split in the reduction reactor, with the reactions occurring being predominantly endothermic. Splitting already occurs in the cooling zone. Ammonia introduced into the cooling zone contributes to cooling on the one hand because it is split endothermically, and on the other hand it contributes to reduction reactions in the reduction reactor.
- the cooling using ammonia can, for example, be regulated so that the temperature of the reduced material removed from the reduction reactor has a desired temperature for further processing. For example, if the hot DRI - HDRI - taken from the reduction reactor is subsequently compacted If necessary, a different temperature should be aimed for than when it is fed to an EAF.
- the device for reducing material containing metal oxide can comprise one or more reduction reactors.
- the device for reducing metal oxide-containing material can include one or more top gas outlets.
- the device for reducing metal oxide-containing material can include one or more supply lines for ammonia contribution; these are suitable for adding liquid ammonia, or suitable for adding gaseous ammonia, or suitable for both adding liquid ammonia and for adding gaseous ammonia, or for adding hydrogen H 2 contained from ammonia by splitting - pure or in one Mixture with nitrogen N2 - suitable.
- the device for reducing material containing metal oxide can comprise one or more supply lines.
- ammonia NH 3 can be used to obtain reducing gas.
- the reducing gas is prepared in the preparation system using ammonia NH 3 .
- the preparation system can include one or more splitting systems for splitting ammonia.
- the preparation system can also include one or more mixing devices which mix ammonia - liquid or gaseous - and/or at least one of its cleavage products hydrogen H 2 and nitrogen N 2 with other components; you can also mix mixtures of the cleavage products with other components.
- the preparation system can also include one or more component supply lines for supplying components used in the preparation of the reducing gas.
- the preparation system can also include one or more separation devices for separating the gas mixture obtained from the splitting of ammonia from hydrogen H 2 and nitrogen N 2 ; Separation does not only mean complete separation, but also enrichment or depletion of hydrogen H 2 or nitrogen N 2 .
- separation devices for separating the gas mixture obtained from the splitting of ammonia from hydrogen H 2 and nitrogen N 2 ; Separation does not only mean complete separation, but also enrichment or depletion of hydrogen H 2 or nitrogen N 2 .
- a supply line for ammonia contribution can open into a line carrying top gas, the opening being to be understood as a mixing device. Reducing gas can therefore be prepared using ammonia and top gas as components.
- a supply line for ammonia contribution can open into a line carrying processing gas, the opening being to be understood as a mixing device.
- reducing gas can be prepared using ammonia and processing gas as components.
- a feed line for ammonia contribution can open into a line carrying precursors of the reducing gas, the mouth being to be understood as a mixing device. This means that reducing gas can be prepared using ammonia.
- the reduction reactor or its bustle is supplied with reducing gas via the supply line, which is created by adding ammonia via a supply line for ammonia contribution into a line carrying top gas.
- the supply line also serves as a preparation system and mixing device, since top gas and ammonia mix as they flow through and the reducing gas is prepared.
- the supply line can also be part of the preparation system in another way; for example, if feed lines for feeding additional components into the precursor gas open into the feed line, or if heating devices are present in the feed line.
- the preparation system includes devices for heating ammonia so that ammonia can be heated before being added to top gas and/or processing gas.
- the top gas removal includes one or more processing plants; Processing gas is then supplied to the preparation system through the top gas outlet.
- the processing systems can be, for example, a dedusting device - dry or wet - or a cooling device, or a compression device, or a heating device, or a cooling device, or a device for adjusting the water vapor content, or a desulfurization device. It is also possible for a processing system to fulfill several processing functions - for example, a cooling device can also act as a device for adjusting the water vapor content.
- the top gas discharge comprises at least one processing system, which is a device for reducing the nitrogen content.
- the nitrogen content of the top gas can thus be reduced and a processing gas can be provided with a reduced nitrogen content compared to top gas.
- This can be, for example, a device for reducing the nitrogen content different permeation rates, a device for reducing the nitrogen content using different adsorption forces - such as pressure swing adsorption -, a device for reducing the nitrogen content using different boiling temperatures.
- a natural gas feed line for example, a natural gas feed line, a hydrogen feed line, a carbon monoxide feed line, a coke oven gas feed line, a syngas feed line, a hydrocarbon feed line.
- One or more or all feed lines can also be suitable for feeding several group members, for example a natural gas/syngas/coke oven gas feed line.
- the reduction reactor has a cooling zone and/or a product cooler, and an ammonia feed line opens into the cooling zone and/or the product cooler.
- Another subject of the present application is a signal processing device with a machine-readable program code, characterized in that it has control commands for carrying out a method according to the invention.
- Another item is a signal processing device for carrying out the method according to one of claims 1 to 7.
- Another subject of the present application is a machine-readable program code for a signal processing device, characterized in that the program code has control commands which cause the signal processing device to carry out a method according to the invention.
- a further subject is a computer program product comprising instructions for a signal processing device which, when the program is executed for the signal processing device, cause the signal processing device to carry out the method according to one of claims 1 to 7.
- Another subject of the present application is a storage medium with a machine-readable program code according to the invention stored thereon.
- Another object is a storage medium with a computer program stored thereon for carrying out the method according to one of claims 1 to 7.
- Figure 1 shows schematically the implementation of a method according to the invention in a device 1 according to the invention for the reduction of material containing metal oxide.
- Metal oxide-containing material 3, here iron oxide-containing material, is introduced into a reduction reactor 2, here a reduction shaft, and forms a fixed bed 4 there.
- reducing gas is used to reduce the metal oxide-containing material 3 in the reduction reactor 2.
- Top gas is removed from the reduction reactor 2 by means of top gas discharge 5.
- the top gas outlet 5 flows into the preparation system 6 for preparing reducing gas.
- a supply line for ammonia contribution 7 flows into the preparation system 6.
- reducing gas is prepared using ammonia NH 3 and using top gas as a component.
- the reducing gas obtained using ammonia and top gas is fed via the supply line 8 to the reduction reactor 2 containing the metal oxide-containing material 3.
- top gas is mixed with ammonia, and the resulting gas mixture is the reducing gas.
- the top gas is therefore used directly when preparing the reducing gas.
- FIG 2 shows largely analogous to Figure 1 schematically a variant in which the top gas is used indirectly during the preparation of the Reducing gas is used.
- the preparation system 6 is supplied with processing gas via the top gas outlet 5.
- the processing gas is obtained by processing the top gas;
- In the top gas discharge there is a device for reducing the nitrogen content 9; a nitrogen-depleted stream of processing gas is fed to the preparation system via the top gas discharge 5.
- the processing gas is mixed with ammonia, and the resulting gas mixture is the reducing gas.
- a portion of the top gas is used as a component in the preparation of the reducing gas.
- Figure 3 shows largely analogous to Figure 2 schematically a variant in which the preparation system 6 includes a feed line for natural gas 10. This makes it possible to add natural gas to the resulting gas mixture after combining processing gas and ammonia, or to add ammonia to the resulting gas mixture after combining processing gas and natural gas.
- the resulting gas mixture can serve as a precursor of the reducing gas and can be converted into reducing gas in a reformer, not shown.
- Figure 4 shows largely analogous to Figure 2 schematically a variant in which an ammonia supply line 11 opens into the cooling zone 12 of the reduction reactor 2. This allows ammonia to be introduced into the cooling zone during the direct reduction in the reduction reactor 2.
- Figure 5 shows largely analogous to Figure 1 schematically a variant in which the bustle 13 of the reduction reactor is also shown.
- Reducing gas is supplied to the bustle 13 via supply line 8.
- ammonia is fed into the line 14 carrying top gas via a feed line for ammonia contribution 7.
- the supply line 8 also counts as a preparation system and as a mixing device, as ammonia and top gas are mixed in it.
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/EP2023/058112 WO2023186967A1 (fr) | 2022-03-30 | 2023-03-29 | Réduction d'un matériau à teneur en oxyde métallique à base d'ammoniac nh3 |
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EP22165598 | 2022-03-30 |
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EP22194331.9A Pending EP4253572A1 (fr) | 2022-03-30 | 2022-09-07 | Réduction à base d'ammoniac nh3 de matériau contenant de l'oxyde métallique |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013216929A (ja) * | 2012-04-05 | 2013-10-24 | Jfe Steel Corp | 還元鉄の冷却方法 |
CN112813219A (zh) * | 2021-02-05 | 2021-05-18 | 辽宁科技大学 | 一种氨气直接还原铁实现近零排放的系统及工艺 |
WO2021241272A1 (fr) * | 2020-05-28 | 2021-12-02 | 日本製鉄株式会社 | Procédé de production de fer réduit |
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2022
- 2022-09-07 EP EP22194331.9A patent/EP4253572A1/fr active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013216929A (ja) * | 2012-04-05 | 2013-10-24 | Jfe Steel Corp | 還元鉄の冷却方法 |
WO2021241272A1 (fr) * | 2020-05-28 | 2021-12-02 | 日本製鉄株式会社 | Procédé de production de fer réduit |
CN112813219A (zh) * | 2021-02-05 | 2021-05-18 | 辽宁科技大学 | 一种氨气直接还原铁实现近零排放的系统及工艺 |
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