Classifications

• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21B—MANUFACTURE OF IRON OR STEEL
  • C21B13/00—Making spongy iron or liquid steel, by direct processes
  • C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21B—MANUFACTURE OF IRON OR STEEL
  • C21B13/00—Making spongy iron or liquid steel, by direct processes
  • C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
  • C21B13/029—Introducing coolant gas in the shaft furnaces
• • 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
  • C21B2100/22—Increasing the gas reduction potential of recycled exhaust gases by reforming
• • 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
  • C21B2100/40—Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
  • C21B2100/44—Removing particles, e.g. by scrubbing, dedusting
• • 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
  • C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
  • C21B2100/64—Controlling the physical properties of the gas, e.g. pressure or temperature
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
  • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
  • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen

Definitions

• the present invention relates to the production of iron by direct reduction.
• direct-reduction processes Processes that produce iron by reduction of iron oxide in iron ore below the melting point of the iron produced are known as direct-reduction processes.
• the product thereby obtained is known as direct-reduced iron or DRI. Due to its structure with a very high specific surface area, direct-reduced iron is also referred to as sponge iron.
• DRI is often compacted into denser briquettes referred to in the art as hot briquetted iron or HBI.
• HBI hot briquetted iron
• Direct reduction processes whereby iron ore is subjected to direct reduction in contact with a reducing gas which is produced inside the iron-ore-reduction zone of the reactor or installation are known in the art.
• a further known example of a process whereby coal is used to produce reducing gas inside the direct-ore-reduction zone of a shaft furnace is the Midrex EDR process whereby iron ore, coal and limestone are introduced at the top of the shaft furnace, which is heated by electrodes in the walls of the furnace.
• the DRI, the char and the spent limestone are collected at the bottom of the shaft furnace.
• the steel industry is a major contributor of CO 2 emissions. This is especially true for traditional ironmaking by means of blast furnaces. Compared to iron production in a blast furnace followed by steel production in a converter, steel production by direct iron-ore reduction and subsequent melting in an Electric Arc Furnace (EAF) generates lower levels of CO 2 emissions.
• EAF Electric Arc Furnace
• MIDREX NG TM process In order to reduce the CO 2 emissions generated during DRI production, processes such as MIDREX NG TM process (whereby “NG” refers to natural gas) have been proposed.
• NG refers to natural gas
• iron ore is subjected to direct reduction in contact with a reducing gas which is produced upstream of the iron-ore-reduction reactor or furnace, for example by reforming natural gas in a reformer upstream of the iron-ore-reduction reactor or furnace.
• the abovementioned known and projected processes are continuous iron-ore reduction processes.
• Direct-reduction processes are of interest in regions, which, depending on the raw material used to generate reducing gas, have access to suitable iron ores and inexpensive resources of non-coking coals, natural gas, and/or renewable energy, such as hydroelectric power.
• Hydrogen can in principle be produced at any location with access to water and power.
• the number of locations disposing of sufficient energy sources for the production of hydrogen on an industrial scale are limited and often located far away from deposits of iron ore suitable for direct reduction and/or industrial basins. This is more specifically the case for energy sources of renewable energy, which are required for the production of green hydrogen.
• a recent example of a direct-ore-reduction method with in-situ generation of a reducing gas is described in CN-A-112921143.
• Said method uses gaseous ammonia for the production of reducing gas inside a vertical batch-type furnace which contains the iron ore.
• the disclosed method specifically includes the following steps:
• This process is thus a batch process.
• ammonia is easier and cheaper to store and transport safely.
• the use of ammonia could therefore contribute to increasing the geographic spread of DRI processes, in that low-carbon-footprint ammonia could be produced in locations where large amounts of renewable energy are available. This ammonia could then be transported to iron-ore-reduction reactors or furnaces at different locations for use as a source of reducing gas in the direct-reduction process.
• a process for the continuous direct reduction of iron ore takes place in a direct-reduction unit which comprises at least:
• Iron ore and reducing gas are supplied to the direct-ore-reduction zone of the unit (step a).
• the reducing gas contains one or more reducing agents.
• step b the iron ore is in direct contact with the reducing gas.
• the iron ore is subjected to reduction with the one or more reducing agents. DRI is thus obtained (step b).
• the obtained DRI is transferred from the direct-ore-reduction zone of the unit to the iron-collection zone thereof (step c).
• ammonia is supplied to the iron-collection zone. Inside said iron-collection zone, the ammonia comes into contact with the DRI and, as a consequence thereof, the ammonia undergoes the following catalytic dissociation reaction (reaction (1)) inside said iron-collection zone:
• step d nitrogen and hydrogen are produced.
• the hydrogen produced (in combination with nitrogen) by the ammonia dissociation reaction is thus supplied as reducing gas to the direct-ore-reduction zone as described with respect to step a of the process.
• the hydrogen intervenes as a reducing agent in the direct reduction of the iron ore as described earlier with respect to step b of the process.
• the iron ore may in particular be supplied to the DRI reactor in the form of lumps and/or pellets.
• the produced nitrogen does not chemically intervene in the direct reduction of the iron ore.
• the nitrogen leaves the direct-ore-reduction unit without undergoing chemical reaction.
• the nitrogen is thus not a reducing agent and acts as a ballast gas during the direct-reduction reaction.
• Nm 3 is a better heat carrier per Nm 3 , Nm 3 being defined as the amount of gas which occupies a cubic metre at a temperature of 0°C and at an absolute pressure of 1 atm. Since the reduced, partially reduced and unreduced iron ore in the reactor relies on the hot reducing gases to provide heat, nitrogen can hold more heat (at a given temperature) than 100% H 2 and therefore it provides thermal ballast to the process.
• the gas atmosphere inside the direct-ore-reduction zone is reducing in nature. Said atmosphere is therefore not conducive to NOx formation, NOx being an environmentally highly undesirable pollutant.
• the direct-ore-reduction zone is advantageously located at a higher level than the iron-collection zone. In this manner, the DRI can be transferred from the direct-ore-reduction zone, where it is produced, to the lower iron-collection zone by gravity.
• the nitrogen and hydrogen produced in the iron-collection zone is advantageously transferred to the direct-ore-reduction zone under the effect of an upward draft within the direct-reduction unit.
• the direct-ore-reduction zone is located in an ore-reduction chamber and the iron-collection zone is located in a separate iron-collection chamber.
• means are provided, on the one hand, for transferring direct-reduced iron from the ore-reduction chamber to the iron-collection chamber and, on the other hand, for transferring the nitrogen- and hydrogen-containing reducing gas from the iron-collection chamber to the ore-reduction chamber.
• the unit may comprise a first duct or chute for transferring the direct-reduced iron from the ore-reduction chamber to the iron-collection chamber and a (second) duct for transferring the produced nitrogen- and hydrogen-containing reducing gas in the opposite direction from the iron-collection chamber to the ore-reduction chamber.
• a same duct may be used for both material transfers.
• the ore-reduction chamber is a moving-bed shaft reactor.
• Countercurrent moving-bed shaft furnaces in which the gas phase flows in countercurrent with the solid charge of iron ore and DRI are particularly useful examples of such a moving-bed shaft furnace.
• the direct-ore-reduction zone and the iron-collection zone are preferably distinct, i.e. separate, zones located within a common reactor shell.
• the direct-ore-reduction zone and the iron-collection zone are located within a same moving-bed shaft reactor, with the direct-ore-reduction zone being located above the iron-collection zone.
• iron ore is fed to the direct-ore-reduction zone at the top of the shaft reactor.
• the iron ore travels downwards inside the shaft reactor, while progressively undergoing reduction in contact with the upwardly travelling reducing gas.
• the spent reducing gas is evacuated from the shaft reactor at or near the upper end of the shaft reactor. From the direct-ore-reduction zone, the produced DRI travels further downward to the iron-collection zone as part of the moving bed.
• the ammonia is supplied to the iron-collection zone in such a way as to enter in intimate contact with the DRI. Thereto, the ammonia is typically supplied to the lower half of the iron-collection zone.
• the injection of the ammonia into the iron-collection zone is preferably distributed around the circumference of the shaft reactor at the level of the iron-collection zone, for example by means of a bustle pipe and multiple tuyeres.
• the direct-reduction unit may further comprise a DRI-cooling zone in which the DRI is cooled after having participated in the ammonia dissociation reaction.
• the process according to the present invention further comprises a step of transferring the DRI from the iron-collection zone to the iron-cooling zone (step f) and a step of cooling the DRI inside said iron-cooling zone (step g).
• a cooling gas may advantageously be used for cooling the DRI in the iron-cooling zone.
• the iron-cooling zone may be located in a separate cooling chamber.
• the iron-collection zone and the iron-cooling zone may be separate zones located within a common reactor shell.
• the direct-ore-reduction zone, the iron-collection zone and the iron-cooling zone are separate, i.e. distinct, zones within a same shaft reactor, such as a same moving-bed shaft reactor.
• the DRI produced in the direct-ore-reduction zone travels, as part of the moving bed, first from the direct-ore-reduction zone to the iron-collection zone and then from the iron-collection zone into the iron-cooling zone.
• the ammonia dissociation reaction is an endothermic reaction
• the ammonia is supplied to the iron-collection zone in such a way that the ammonia comes into contact with the DRI inside the iron-collection zone before the DRI is transferred from the iron-collection zone to the iron-cooling zone in step f and thus also before the DRI is cooled in step g of the process.
• cooling gas may be injected into the iron-cooling zone, while the spent cooling gas is again extracted from the iron-cooling zone by forced extraction.
• the ammonia may be injected into the iron-reduction unit either as pure ammonia or as part of a mixture, in particular a mixture that includes one or more additional reducing-gas precursors, such as gaseous hydrocarbons (such as natural gas), CO 2 and H 2 O and/or one or more additional reducing agents, in particular H 2 and CO.
• additional reducing-gas precursors such as gaseous hydrocarbons (such as natural gas), CO 2 and H 2 O and/or one or more additional reducing agents, in particular H 2 and CO.
• additional reducing gas containing one or more reducing agents
• additional reducing agents may be supplied to the direct-reduction unit in order to optimise the ore reduction and/or to adjust the properties of the produced DRI product that contains carbon. Carbon is very helpful to the electric arc furnace melting process.
• Hydrogen not generated by ammonia dissociation in the iron-collection zone may be used as additional reducing gas/agent.
• This supplementary hydrogen preferably has a low carbon footprint, for example, hydrogen produced by electrolysis with electricity from renewable energy sources, in particular blue or green hydrogen.
• Another useful source of supplementary hydrogen as an additional reducing agent is coke oven gas.
• syngas is preferably generated by dry reforming or steam reforming of hydrocarbons, in particular gaseous hydrocarbons such as CH 4 /natural gas, preferably by catalytic dry reforming or catalytic steam reforming.
• Syngas can also be generated by partial combustion of hydrocarbon, preferably with industrially pure oxygen as the combustion oxidant, i.e. oxygen with a purity of at least 90%vol and upto 100%vol.
• Coke oven gas and syngas may thus be used as additional reducing gases.
• Coke oven gas and syngas moreover also contain CO, which is also useful as an additional reducing agent for the direct reduction of the iron oxides in the iron ore.
• Coke oven gas also contains hydrocarbons that are reformed in the presence of CO 2 and or H 2 O to produce additional CO and H 2 as additional reducing agents. These hydrocarbons therefore act as a precursor for these additional reducing agents.
• top gas or flue gas refers to the spent reducing gas which is evacuated from the direct-ore-reduction zone after having been used for the reduction of iron ore in said zone.
• the top gas will also contain CO.
• CO or a CO-containing gas may also be used as additional reducing gas in the process according to the invention, with CO as an additional reducing agent in addition to the H 2 generated by the dissociation of ammonia.
• the top gas will also contain CO.
• recycled top gas from the direct-reduction unit can be used as a further useful source of CO as an additional reducing agent.
• CO-containing gas such as coke oven gas and/or syngas and/or recycled top gas may thus be mixed with the ammonia-containing stream.
• additional reducing agent in particular H 2 and/or CO may also be generated inside the direct-reduction unit itself by processes other than the dissociation of ammonia as described above.
• syngas which contains both CO and H 2
• syngas which contains both CO and H 2
• a precursor or precursor combination for the additional reducing agent other than ammonia
• a precursor or precursor combination for the additional reducing agent is typically supplied to the iron-collection zone of the direct-reduction reactor. Inside the iron-collection zone, the precursor or precursor combination is then reformed to produce one or more additional reducing agents.
• the thus produced additional reducing agent(s) is/are transferred, together with the N 2 and H 2 produced by the ammonia dissociation reaction, from the iron-collection zone to the direct-ore-reduction zone as described earlier.
• the hydrogen produced by dissociation of ammonia and the one or more additional reducing agents each participate in the reduction of the iron ore to metallic iron.
• the precursor or precursor combination may be supplied to the iron-collection zone in the form of a mixture with the supplied ammonia and/or separately from the supplied ammonia.
• gaseous hydrocarbon such as CH 4 /natural gas is advantageously supplied to the iron-collection zone as a precursor, preferably in combination with CO 2 (when syngas is to be produced by so-called ‘dry reforming’) or in combination with steam (when syngas is to be produced by so-called ‘steam reforming’).
• syngas i.e. syngas produced upstream of the direct-reduction unit
• syngas may also be supplied to the process as an additional reducing agent for the direct reduction of iron ore.
• top gas from the direct-reduction unit may be recycled as an additional reducing gas.
• top gas can also be used as heating fuel.
• top gas may be burnt in order to heat the reformer.
• heat generated by the combustion of top gas may also be used to preheat the ammonia / additional reducing gas / precursors or precursor combinations of additional reducing agents before these are supplied to the direct-reduction unit as disclosed above.
• water is optionally removed from the top gas, typically by condensation, before the top gas is used as fuel and/or recycled as reducing gas.
• CO 2 may or may not also be removed from the top gas before the top gas is used as fuel and/or recycled as reducing gas, in particular before the top gas is recycled as reducing gas. Whether or not such CO 2 -removal is appropriate depends on the particular circumstances of the process. For example, if, in addition to ammonia dissociation, syngas is to be produced inside the iron-collection zone, CO 2 present in the recycled top gas (portion) may be effectively used for reforming hydrocarbons to syngas in said zone.
• Additional reducing gas/agent may, in particular be introduced directly into the direct-ore-reduction zone of the unit, i.e. without first passing through the iron-collection zone.
• additional reducing gas/agent may be supplied to the iron-collection zone of the unit and be transferred, together with the produced N 2 and H 2 , from the iron-collection zone to the direct-ore-reduction zone.
• the additional reducing gas/agent may be supplied to the iron-collection zone in the form of a mixture with the ammonia or separate therefrom, or even partially mixed with the ammonia and partially separately from the ammonia.
• the supply to the direct-reduction reactor of a carbon-containing additional reducing agent, such as CO, reducing agent precursor or precursor combination, such as a gaseous hydrocarbons or a CO 2 -containing combination, can in particular be useful for the production of DRI which contains carbon or which presents an increased level of carbon, the presence of such carbon in the DRI being, for example, helpful when the DRI is used to produce steel in an electric-arc furnace melting process.
• a carbon-containing additional reducing agent such as CO, reducing agent precursor or precursor combination
• gaseous hydrocarbons which may be used as reducing agent precursor or precursor combinations are hydrocarbons selected from the group consisting of methane, ethane, propane, butane and pentane, or a combination of two or more of said hydrocarbons, preferably natural gas.
• the present invention also relates to a process for producing steel.
• direct-reduced iron is produced from iron ore by means of any embodiment of the process described above and steel is produced from said direct-reduced iron in an electric arc furnace, including, for example, a form of electric arc furnace that is known in the art as a submerged arc furnace, or by a steel-production process in which direct-reduced iron is melted in another DRI melting device for producing steel, optionally after the direct-reduced iron (30) has been briquetted.
• the direct-reduced iron may be briquetted before being used in the production of steel.
• the direct-reduction unit is in the form of a moving bed DRI reactor 1, whereby the iron ore 2 is fed to DRI reactor 1 at the top of the reactor and then travels downwards inside DRI reactor 1.
• the ore enters upper direct-ore-reduction zone 4a where the ore is reduced, at a temperature below the melting point of iron, to direct-reduced iron (DRI) 4 through contact with reducing gas 3a, containing the reducing agent hydrogen.
• DRI direct-reduced iron
• Said reduction of iron ore 2 with hydrogen as reducing agent includes the following reactions:
• the DRI 4 thus produced travels, at a temperature of between 750°C and 1050°C, more preferably between 850°C and 950°C, further down to the iron-collection zone 4b positioned immediately below direct-iron-reduction zone 4a.
• the temperature at which the reducing gas is supplied to the iron-collection zone 4b is preferably at least equal to and more preferably higher than the temperature of the DRI supplied to the iron-collection zone 4b.
• the reducing gas is advantageously supplied to the iron-collection zone 4b at a temperature between 850°C and 1100°C, more preferably between 950°C and 1050°C.
• the DRI 4 leaving direct-ore-reduction zone 4b practically contains a mixture of unreduced iron oxides, partially reduced iron oxides and metallic iron, i.e. fully reduced iron oxide.
• iron content in the DRI product is metallic iron with the remaining iron being in the form of non-metallic iron oxide (FexOy).
• the DRI 4 is used as a catalyst for the production of reducing gas.
• a preheated ammonia-containing gas stream 25c is supplied to iron-collection zone 4b via bustle pipe 3, which acts as a manifold for distributing gas stream 25c and from which multiple injectors (not shown), evenly distributed around the circumference of DRI reactor 1, lead into iron-collection zone 4b.
• Gas feed stream 25c contains ammonia 19 in a proportion of stream 25c of more than 0%vol and upto 100%vol, preferably between 50%vol and 100%vol.
• ammonia dissociation also referred to as ammonia cracking, takes place. More specifically, the ammonia 19 of gas stream 25c, undergoes dissociation reaction (1):
• the ammonia dissociation reaction As hydrogen acts as a reducing agent for the reduction of iron ore 2, the ammonia dissociation reaction generates a reducing gas 3a containing said hydrogen as a reducing agent.
• the thus generated reducing gas 3a travels upwards from the iron-collection zone 4b to the direct-ore-reduction zone 4a, where reducing gas 3a comes into contact with the descending iron ore 2.
• This contact causes the reduction of iron oxide in iron ore 2 into mixture 4 of unreduced iron oxides, partially reduced iron oxides and fully reduced iron oxides, i.e. metallic iron at a temperature below the melting point of the iron (as described above).
• This mixture is referred to as direct reduced iron or DRI 4.
• the DRI is cooled with cooling gas 27 to a temperature which depends on the immediate use of evacuated DRI 30 after its evacuation from DRI reactor 1.
• evacuated DRI 30 is to be charged immediately to an adjacent EAF (not shown) at a temperature ranging between 400°C and 800°C, more preferably between 600°C and 800°C, it is advantageous to limit the cooling to that necessary for safe transport of DRI 30 to the EAF while taking advantage of the sensible heat already/still present in evacuated DRI 30.
• DRI 30 may be cooled to significantly lower temperatures, closer to the ambient temperature, for the storage and/or transport of the DRI.
• the DRI 4 is subjected to limited cooling, for example inside iron-cooling zone 26, before evacuated DRI 30 is formed into briquettes (HBI).
• HBI briquettes
• Cooling gas 27 can be substantially inert so as not to react with hot DRI 4. Cooling gas 27 can also be or contain a gas that imparts desired properties to the DRI 4 while it cools.
• An example of such a gas is natural gas which can crack in accordance with reaction (b) to deposit carbon into the DRI 4 where it dissolves in the iron as a solid solution. As mentioned above, carbon imparts operational and energy-saving benefits to the EAF process during melting of the DRI.
• Cooling gas 27 can also include a portion of top gas 5 from DRI reactor 1.
• the spent cooling gas 27 is extracted from the cooling zone 26 as spent cooling gas stream 28, whereafter stream 28 is cooled before being fortified with makeup cooling gas, if necessary, and compressed for reinjection at the bottom of the cooling zone 26.
• the DRI 30 is extracted from DRI reactor 1 at the bottom of the conical cooling zone 26 at a temperature most appropriate for its subsequent use (as explained above).
• ammonia-containing gas feed stream 24 is divided into substreams, which are separately supplied to gas preheater 25.
• gas substreams 24a, 24b are heated so as to obtain preheated gas substreams 25a, 25b at a temperature of, for example, between 750°C and 1100°C.
• Preheated substreams 24a and 25b are then recombined to form preheated ammonia-containing gas stream 25c, which is supplied to the iron-collection zone 4b of DRI reactor 1.
• feed stream 24 may be supplied to gas preheater 25 without being divided into substreams or may be divided into more than two substreams before being supplied to gas preheater 25.
• Preheater 25 is, in this particular case, heated by combustion of an optionally dewatered fraction 11 of the top gas 5 evacuated from DRI reactor 1.
• gas feed stream 25c may further comprise a hydrocarbon-containing gas 20, such as natural gas or coke oven gas or a mixture thereof.
• a hydrocarbon-containing gas 20 such as natural gas or coke oven gas or a mixture thereof.
• the proportion of each of natural gas and coke oven gas in hydrocarbon-containing gas 20 can be between 0 and 100%vol.
• the proportion of hydrocarbon-containing gas 20 in stream 25c can vary between 0%vol and 50%vol.
• Gas feed stream 25c may also contain additional gaseous hydrogen 21 (such as grey H 2 , preferably blue H 2 and more preferably green H 2 ) in particular in a proportion of between 0%vol and 50%vol of stream 25c.
• Green H 2 is H 2 produced with zero CO 2 emissions, for example through water electrolysis using renewable power.
• Blue H 2 presents an emission intensity of up to 0.97 kg CO 2 / kg H 2 and may, for example, be produced by steam methane reforming with carbon capture.
• Grey H 2 has an emission intensity of up to 9.3 kg CO 2 / kg H 2 and may be produced by steam methane reforming without carbon capture.
• Gas feed stream 25c may also contain additional steam 22. Such additional steam may be added so as to provide a suitable amount of hydrogen in stream 25c for reforming any gaseous hydrocarbon-containing gas 20 (such as natural gas and/or coke-oven gas) contained therein inside the iron-collection zone 4b of DRI reactor 1.
• gaseous hydrocarbon-containing gas 20 such as natural gas and/or coke-oven gas
• Gas feed stream 25c may also contain syngas 23 in proportion of stream 25c that can vary between 0%vol and 50%vol.
• Gas feed stream 25c may also contain any other gas, such as recycled top gas 10a, that can be advantageously added in order to improve the efficiency of reducing-gas production in iron-collection zone 4b or, more generally, in order to improve the efficiency of the ore reduction inside direct-ore-reduction zone 4a, and/or, as mentioned earlier, to promote or cause carbon deposition on the produced DRI 4.
• recycled top gas 10a any other gas, such as recycled top gas 10a, that can be advantageously added in order to improve the efficiency of reducing-gas production in iron-collection zone 4b or, more generally, in order to improve the efficiency of the ore reduction inside direct-ore-reduction zone 4a, and/or, as mentioned earlier, to promote or cause carbon deposition on the produced DRI 4.
• iron-collection zone 4b When preheated gas stream 25c contains at least one hydrocarbon, such as methane, said hydrocarbon is subjected to reforming in iron-collection zone 4b.
• iron-collection zone 4b may act as a steam reformer or as a dry reformer for said hydrocarbon (see reactions (a)) and (.c) or (f.)).
• the DRI 4 present in the iron-collection zone 4b acts as a catalyst during hydrocarbon reforming.
• the H 2 - and CO-containing syngas which is produced by hydrocarbon reforming travels from iron-collection zone 4b to the direct-ore-reduction zone 4a together with the ammonia dissociation products 3a.
• both the H 2 and the CO of the syngas act as additional reducing agents for the reduction of the iron ore 2.
• DRI reactor 1 and in particular its direct-ore-reduction zone 4a, may be equipped with heating means (not shown) in order to maintain iron ore 2 and reducing gas 3a in direct-ore-reduction zone 4a within a temperature range suitable/optimised for the ore-reduction reactions taking place therein.
• the spent reducing gas 5 leaves DRI reactor 1 at or near its top at a temperature between 100°C and 600°C, preferably between 250°C and 500°C and more preferably between 300°C and 450°C.
• gas feed stream 25c may contain recycled top gas 10a.
• evacuated top gas 5 may be dedusted in a dust catcher and/or scrubber 6.
• the optionally dedusted top gas 6a then travels to a heat recovery system 7 where the temperature of the top gas is reduced in a controlled manner to a setpoint temperature between 25°C and 100°C but preferably between 25°C and 40°C.
• the chosen setpoint temperature can be, but is not necessarily, selected to regulate the partial pressure of water in the recycled top gas 10a (see hereafter).
• the energy recovered in heat recovery system 7 can be used for any of a variety of purposes, for example, without limitation, for making steam or for preheating combustion oxidant and/or fuel(s) that may be used in gas preheater 25.
• the cooled top gas 7a is optionally dewatered in condenser 8 to produce dewatered and cooled top gas stream 8a.
• a CO 2 -separation step 10 is normally used to improve the steam reforming process.
• CO 2 -separation step 10 may also be omitted or the amount of CO 2 removed from stream 9 in step 10 may be limited because CO 2 participates in the reaction (c) and thus contributes to the production of reducing gas in iron-collection zone 24b. In that case, due care will be taken to avoid or limit reaction (b).
• At least a fraction of said dewatered and cooled top gas stream 8a is compressed in compressor 9, after which CO 2 is removed from compressed top gas 9a in CO 2 -removal unit 10.
• Stream 9a needs to be at pressures between 2 and 10 Bar, preferably between 4 and 8 Bar in order to separate CO 2 from stream 9a using a vacuum pressure swing adsorption (VPSA) machine or a pressure swing adsorption (PSA) machine to produce a CO 2 -lean stream 10a.
• VPSA vacuum pressure swing adsorption
• PSA pressure swing adsorption
• a further option is to separate CO 2 from stream 9a using a chemical absorption unit to produce a CO 2 -lean stream 10a, for example through the use of amines. This can be performed at lower pressures if needed.
• CO 2 can also be separated from stream 9a by means of polymeric membranes or through cryogenic separation.
• a CO 2 -separation step 10 may also be omitted or the amount of CO 2 removed from stream 9 in step 10 may be limited because CO 2 advantageously contributes to the production of reducing gas if an upstream gas reformer is used to produce stream 23, and participates in the reaction (c).
• CO 2 -removal depends inter alia (a) on the concentration of CO 2 present in top gas 5, which in turn depends on the nature and relative amounts of the gases (other than cooling gas 27, which is extracted from cooling zone 26 of DRI reactor 1) which are supplied to DRI reactor 1, and (b) on whether and to what extent the presence of CO 2 in gas feed stream 25c is useful, for example for the purpose of hydrocarbon reforming inside iron-collection zone 4b of DRI reactor 1.
• the resulting treated top gas 10a is, in the illustrated embodiment, then mixed with the other ingredients of gas feed stream 25c.
• Top gas 5 may, however, also be used as a heating fuel, instead of or in addition to addition thereof to gas feed stream 25c.
• cooled and dewatered top gas stream 8a may be split into recycle substream 9 and additional substream 11.
• the flow rate of substream 11 can be between 0 and 100%vol of stream 8a, but is preferably between 20%vol and 90%vol of stream 8a and more preferably between 30%vol and 80%vol of stream 8a.
• substream 11 is used as fuel for preheating gas stream 24 so as to obtain preheated feed stream 25c.
• Combustible gas, such as natural gas 8b and/or even ammonia 8c may be added to stream 11 as needed to modify the heating value of stream 11.
• This preheating takes place in heater 25 which comprises multiple combustion chambers 11a, 11b, 11c, and multiple flow paths for the gas to be heated, said flow paths being separated from the combustion chambers by heat-exchange walls.
• gas stream 24 is divided into individual substreams 24a and 24b. Each substream 24a, 24b is made to flow along its separate flow path through heater 25.
• Top gas substream 11 is similarly divided over the individual combustion chambers 11a, 11b and 11c of heater 25 and burnt therein with a suitable oxidant. In this manner, heat is generated in each combustion chambers 11a, 11b and 11c and said heat is used to heat the individual substreams 24a, 24b into heated substreams 25a, 25b, which are then combined to obtain preheated gas feed stream 25c.
• combustion flue gases 13a, 13b and 13c exiting combustion chambers 11a, 11b and 11c are passed through optional heat exchanger 12 to preheat stream 11 and to produce a cooler flue gas stream 13 before the latter flows to stack 14 where it exits into the atmosphere 15.
• optional heat exchanger 12 to preheat stream 11 and to produce a cooler flue gas stream 13 before the latter flows to stack 14 where it exits into the atmosphere 15.
• the flue gases 13 will contain CO 2 , which should preferably be extracted from stream 13 before its release into the atmosphere 15 (extraction not shown).
• the ammonia 19 of gas feed stream 25c is blue ammonia (synthesised using blue hydrogen) or preferably green ammonia (synthesised using green hydrogen) 19, thus imparting significant reductions in CO 2 emissions/carbon footprint compared to conventional hydrocarbon-based DRI operation.
• Additional gaseous hydrocarbon(s) 23b and/or combustion oxidant, such as oxygen, 23a may be added to gas feed stream 25c upstream of DRI reactor 1 to further adjust the temperature and composition of feed stream 25c before its introduction into the bustle pipe 3 of DRI reactor 1.
• (blue/green) Ammonia can more easily be stored and shipped around the world to regions that do not have the natural resources to produce (blue/green) hydrogen.
• Distinction is made between continuously operated DRI reactors/processes and batch DRI reactors/processes.
• Gas streams injected in the continuously operated DRI reactor are generally injected continuously during operation of the DRI reactor.
• gas-feed stream 25c consisting of green ammonia or of a controlled mixture of green ammonia with natural gas and appropriate amounts of steam is used in the process according to the present invention
• DRI with a controllable carbon content can be produced with reduced CO 2 emissions.

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• 2022
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