WO2022254235A1 - A method for manufacturing direct reduced iron - Google Patents
A method for manufacturing direct reduced iron Download PDFInfo
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- WO2022254235A1 WO2022254235A1 PCT/IB2021/054755 IB2021054755W WO2022254235A1 WO 2022254235 A1 WO2022254235 A1 WO 2022254235A1 IB 2021054755 W IB2021054755 W IB 2021054755W WO 2022254235 A1 WO2022254235 A1 WO 2022254235A1
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- 238000000034 method Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 45
- 230000009467 reduction Effects 0.000 claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000005495 cold plasma Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 13
- 239000000112 cooling gas Substances 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 9
- 235000013980 iron oxide Nutrition 0.000 description 6
- 229910000805 Pig iron Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001567 cementite Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000003134 recirculating effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010744 Boudouard reaction Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
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
- 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
- C21B2100/24—Increasing the gas reduction potential of recycled exhaust gases by shift reactions
-
- 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
Definitions
- the invention is related to a method for manufacturing direct reduced iron.
- Steel can be currently produced through two mains manufacturing routes.
- most commonly used production route consists in producing pig iron in a blast furnace, by use of a reducing agent, mainly coke, to reduce iron oxides.
- a reducing agent mainly coke
- This method both in the production of coke from coal in a coking plant and in the production of the pig iron, releases very significant quantities of C02.
- Produced pig iron is then decarburized, for example in a converter or Basic Oxygen Furnace (BOF) to produce steel which is then refined to get the appropriate composition. This is called the BF-BOF route.
- BOF Basic Oxygen Furnace
- the second main route involves so-called “direct reduction methods”.
- direct reduction methods are methods according to the brands MIDREX, FINMET, ENERGIRON/FIYL, COREX, FINEX etc., in which sponge iron is produced in the form of HDRI (hot direct reduced iron), CDRI (cold direct reduced iron), or HBI (hot briquetted iron) from the direct reduction of iron oxide carriers.
- Sponge iron in the form of HDRI, CDRI, and HBI usually undergo further processing in electric arc furnaces.
- each direct reduction shaft with cold DRI discharge There are 3 zones in each direct reduction shaft with cold DRI discharge: Reduction zone at top, transition/intermediate zone at the middle, cooling zone at the cone shape bottom.
- Reduction zone at top Reduction zone at top
- transition/intermediate zone at the middle cooling zone at the cone shape bottom.
- cooling zone at the cone shape bottom In hot discharge DRI, this bottom part is used mainly for product homogenization before discharge, and control of overall solids follow.
- the reducing gas generally comprises hydrogen and carbon monoxide (syngas) and is obtained by the catalytic reforming of natural gas.
- a transition section is found below the reduction section; this section is of sufficient length to separate the reduction section from the cooling section, allowing an independent control of both sections.
- carburization of the metallized product happens. Carburization is the process of increasing the carbon content of the metallized product inside the reduction furnace through following reactions:
- Injection of natural gas in the transition zone is using sensible heat of the metallized product in the transition zone to promote hydrocarbon cracking and carbon deposition. Due to relatively low concentration of oxidants, transition zone natural gas is more likely to crack to H2 and Carbon than reforming to H2 and CO. Flydrocarbon cracking provides carbon for DRI carburization and, at the same time adds reductant (H2) to the gas that increases the gas reducing potential.
- H2 reductant
- Gas injection is also performed into cooling zone, it usually consists in recirculating cooling gas plus added natural gas.
- Natural gas (NG) addition to cooling gas allows operator to keep the recirculating cooling gas circuit with a high content in methane, otherwise, the predominant component in the cooling gas would be Nitrogen.
- the heat capacity of natural gas is much more than N2: cooling gas recirculating flow is 500-600 Nm3/t with NG, and 800 Nm3/t without NG. Although there will not be too much carbon deposition in cooling zone, but the up flow of cooling gas to higher levels of the furnace will provide more hydrocarbon for cracking.
- the direct reduction route has a lower C02 footprint than the BF-BOF route, the direct reduction process is still a C02 producer.
- the hydrocarbon product is least partly injected into the direct reduction furnace
- the C02-poor stream is re-injected into the furnace as reducing gas
- the C02-rich stream contains between 80 and 100% in volume of carbon dioxide
- an hydrogen stream is supplied to the hydrocarbon production step to react with the C02-rich stream, - the produced hydrocarbon product is a gas which is mixed with the reduction gas before its injection into the furnace,
- the produced hydrocarbon is injected separately from the reducing gas, in the transition zone of the furnace,
- the hydrocarbon chain includes from 1 to 5 carbons
- the hydrocarbon production step is a methanation step
- - the methanation step is a cold plasma reaction
- the invention is also related to a direct reduction plant to perform a method according to the invention comprising a hydrocarbon production unit.
- FIG. 1 illustrates a layout of a direct reduction plant allowing to perform a method according to the invention.
- the direct reduction furnace (or shaft) 1 is charged at its top with oxidized iron 10 in form of ore or pellets. Said iron 10 is reduced into the furnace 1 by a reducing gas 11 injected into the furnace and flowing counter-current from oxidized iron. Reduced iron 12 exits the bottom of the furnace 1 for further processing, such as briquetting before being used in subsequent steelmaking steps. Reducing gas after having reduced iron exits at the top of the furnace as a top reduction gas 20 (TRG).
- TRG top reduction gas 20
- the top reduction gas 20 usually comprises from 15 to 25%v of CO, from 12 to 20%v of C02, from 35 to 55% of H2, from 15 to 25%v of H20, from 1 to 4% of N2. It has a temperature from 250 to 500°C.
- a cooling gas 13 is captured out of the cooling zone of the furnace, subjected to a cleaning step into a cleaning device 30, such as a scrubber, compressed in a compressor 31 and then sent back to the cooling zone of the shaft 1.
- a cleaning device 30 such as a scrubber
- the first stream 21 being poor in C02, is sent to a preparation device 7 where it will be mixed with other gas, optionally reformed and heated to produce the reducing gas 11.
- the preparation device 7 is a reformer.
- the preparation device 7 emits a preparation exhaust gas 27, also called stack gas.
- the C02 recovery device may be an absorption device, an adsorption device, a cryogenic distillation device or membranes. It could also be a combination of those different devices.
- the second stream 22 which is rich in C02 and representing preferably from 1 to 20%v of the top reduction gas 20, is sent to a hydrocarbon production device 6 to be subjected to a hydrocarbon production step.
- This second stream may comprise between 80 and 100%v of C02.
- C02 is first transformed into carbon monoxide CO. This may be done for example through a hydrogenation step, when hydrogen is available in sufficient amount, to produce CO according to the following reaction: C02 + H2 -> CO + H20
- This reaction is the so-called Reverse Water Gas Shift reaction (RGWS).
- RGWS Reverse Water Gas Shift reaction
- This reaction is performed in presence of a catalyst such as ZnAI204 or Fe203/Cr203. It may also be done by a thermochemical transformation such as Boudouard Reaction or methane reforming, by an electrochemical transformation or with a plasma technology.
- CO thus produced in then transformed into hydrocarbons according to Fischer-Tropsch reactions:
- n is an integer superior or equal to land is preferentially from 1 to 5.
- the man skilled in the art know how to choose the right catalyst and process conditions to perform the wanted Fischer-Tropsch reaction and produce the targeted hydrocarbon.
- C02 and H2 contained into the C02-rich stream 22 react to form methane CFI4 according to the following reaction: C02 + 4 H2 -> CH4 + 2H20
- the hydrocarbon production device is a methanation device 6 such as catalytic reactors, bioreactors, cold plasma/DBD reactors or warm plasma reactors.
- H2 stream 40 may be supplied to the hydrocarbon production unit 6.
- This H2 stream may be provided by a dedicated H2 production plant 9, such as an electrolysis plant. It may be a water or steam electrolysis plant. It is preferably operated using CO2 neutral electricity which includes notably electricity from renewable source which is defined as energy that is collected from renewable resources, which are naturally replenished on a human timescale, including sources like sunlight, wind, rain, tides, waves, and geothermal heat. In some embodiments, the use of electricity coming from nuclear sources can be used as it is not emitting CO2 to be produced.
- This H2 stream 40 may also be added to the reducing gas 11.
- the stack gas 27 may also be supplied to the hydrocarbon production unit 6.
- the hydrocarbon product 23 exiting the hydrocarbon production device 6 is reinjected into the furnace 1.
- this hydrocarbon product 23 is a gas which is mixed with the reducing gas in the preparation device.
- stream 25 it is either injected into the furnace together with the reducing gas or injected independently in the transition zone of the furnace.
- stream 26 it is either injected into the furnace together with the cooling gas 13 or injected independently in the cooling zone of the furnace.
- the hydrocarbon product 23 may be in a gaseous and/or in a liquid form. All those embodiments may be combined with one another.
- the hydrocarbon product serves as a carbon supplier for the DRI product.
- carbon content of the Direct Reduced Iron is set from 0.5 to 3 wt.%, preferably from 1 to 2 wt.% which allows getting a Direct Reduced Iron that can be easily handled and that keeps a good combustion potential for its future use.
- the amount of gas sent to the hydrocarbon production device may be controlled according to the amount of carbon needed in the DRI product.
- the method according to the invention allows to reduce the carbon footprint of the direct reduction process by capture and use of the emitted C02. It may also avoid the need of an external source to increase the carbon content into the DRI product.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Iron (AREA)
Abstract
A method for manufacturing direct reduced iron wherein iron ore is reduced in a direct reduction furnace by a reducing gas, the reducing gas exiting the furnace through the top as a top reduction gas. The top reduction gas is captured and at least partly subjected to a CO2 recovery step during which it is divided into two streams, a CO2-rich stream and a CO2-poor stream. The CO2-rich stream is subjected to an hydrocarbon production step to produce an hydrocarbon product.
Description
A method for manufacturing direct reduced iron
[001] The invention is related to a method for manufacturing direct reduced iron.
[002] Steel can be currently produced through two mains manufacturing routes. Nowadays, most commonly used production route consists in producing pig iron in a blast furnace, by use of a reducing agent, mainly coke, to reduce iron oxides. In this method, approx. 450 to 600 kg of coke, is consumed per metric ton of pig iron; this method, both in the production of coke from coal in a coking plant and in the production of the pig iron, releases very significant quantities of C02. Produced pig iron is then decarburized, for example in a converter or Basic Oxygen Furnace (BOF) to produce steel which is then refined to get the appropriate composition. This is called the BF-BOF route.
[003] The second main route involves so-called “direct reduction methods”. Among them are methods according to the brands MIDREX, FINMET, ENERGIRON/FIYL, COREX, FINEX etc., in which sponge iron is produced in the form of HDRI (hot direct reduced iron), CDRI (cold direct reduced iron), or HBI (hot briquetted iron) from the direct reduction of iron oxide carriers. Sponge iron in the form of HDRI, CDRI, and HBI usually undergo further processing in electric arc furnaces.
[004] There are 3 zones in each direct reduction shaft with cold DRI discharge: Reduction zone at top, transition/intermediate zone at the middle, cooling zone at the cone shape bottom. In hot discharge DRI, this bottom part is used mainly for product homogenization before discharge, and control of overall solids follow.
[005] Reduction of the iron oxides occurs in the upper section of the furnace, at temperatures up to 950°C. Iron oxide ores and pellets containing around 30% by weight of Oxygen are charged to the top of a direct reduction shaft and are allowed to descend, by gravity, through a reducing gas. This reducing gas is entering the furnace from the bottom of reduction zone and flows counter-current from the charged oxidised iron. Oxygen contained in ores and pellets is removed in stepwise reduction of iron oxides in counter-current reaction between gases and oxide. Oxidant content of gas is increasing while gas is moving to the top of the furnace.
[006] The reducing gas generally comprises hydrogen and carbon monoxide (syngas) and is obtained by the catalytic reforming of natural gas. For example, in the so-called MIDREX method, first methane is transformed into a reformer according to the following reaction to produce the syngas or reduction gas: CH4 + C02 = 2CO + 2H2 and the iron oxide reacts with the reduction gas, for example according to the following reactions:
3Fe203 + CO/H2 -> 2Fe304+C02/H20 Fe304 + CO/H2 -> 3 FeO + C02/H20 FeO + CO/H2 -> Fe + CO2/H20
At the end of the reduction zone the ore is metallized.
[007] A transition section is found below the reduction section; this section is of sufficient length to separate the reduction section from the cooling section, allowing an independent control of both sections. In this section carburization of the metallized product happens. Carburization is the process of increasing the carbon content of the metallized product inside the reduction furnace through following reactions:
3Fe + CH4 Fe3C + 2H2 3Fe + 2CO Fe3C + C02 3Fe + CO + H2 Fe3C + H20
[008] Injection of natural gas in the transition zone is using sensible heat of the metallized product in the transition zone to promote hydrocarbon cracking and carbon deposition. Due to relatively low concentration of oxidants, transition zone natural gas is more likely to crack to H2 and Carbon than reforming to H2 and CO. Flydrocarbon cracking provides carbon for DRI carburization and, at the same time adds reductant (H2) to the gas that increases the gas reducing potential.
[009] Gas injection is also performed into cooling zone, it usually consists in recirculating cooling gas plus added natural gas. Natural gas (NG) addition to cooling gas allows operator to keep the recirculating cooling gas circuit with a high content in methane, otherwise, the predominant component in the cooling gas would be Nitrogen. The heat capacity of natural gas is much more than N2: cooling gas
recirculating flow is 500-600 Nm3/t with NG, and 800 Nm3/t without NG. Although there will not be too much carbon deposition in cooling zone, but the up flow of cooling gas to higher levels of the furnace will provide more hydrocarbon for cracking. [0010] As can be seen from above reactions, even if the direct reduction route has a lower C02 footprint than the BF-BOF route, the direct reduction process is still a C02 producer.
[0011] There is a need for a method allowing to further reduce carbon emissions.
[0012] There is also a need for a method allowing to increase carbon content in the DRI product without necessity of an external carbon source. Content of carbon in the DRI product is a key parameter at it plays an important role into the subsequent steps but it also helps to improve the transportability of the DRI product.
[0013] This problem is solved by a method according to the invention, wherein iron ore is reduced in a direct reduction furnace by a reducing gas, the reducing gas exits the furnace through the top as a top reduction gas, this top reduction gas is then captured and at least partly subjected to a C02 recovery step during which it is divided into two streams, a C02-rich stream and a C02-poor stream, the C02-rich stream being subjected to an hydrocarbon production step to produce an hydrocarbon product.. [0014] The method of the invention may also comprise the following optional characteristics considered separately or according to all possible technical combinations:
- the hydrocarbon product is least partly injected into the direct reduction furnace,
- the C02-poor stream is re-injected into the furnace as reducing gas, - the C02-rich stream contains between 80 and 100% in volume of carbon dioxide,
- from 1 to 20% in volume of said top reduction gas is subjected to the hydrocarbon production step,
- an hydrogen stream is supplied to the hydrocarbon production step to react with the C02-rich stream,
- the produced hydrocarbon product is a gas which is mixed with the reduction gas before its injection into the furnace,
- the produced hydrocarbon is a liquid,
- the produced hydrocarbon is injected separately from the reducing gas, in the transition zone of the furnace,
- the produced hydrocarbon is injected with the cooling gas in the cooling zone of the furnace,
- the hydrocarbon chain includes from 1 to 5 carbons,
- the hydrocarbon production step is a methanation step, - the methanation step is a cold plasma reaction,
- prior to its injection into the direct reduction furnace, the reducing gas is heated in a reducing gas preparation step, said reducing gas preparation step emitting a preparation exhaust gas which is at least partly supplied to the hydrocarbon production step [0015] The invention is also related to a direct reduction plant to perform a method according to the invention comprising a hydrocarbon production unit.
[0016] Other characteristics and advantages of the invention will emerge clearly from the description of it that is given below by way of an indication and which is in no way restrictive, with reference to the appended figures in which: - Figure 1 illustrates a layout of a direct reduction plant allowing to perform a method according to the invention
[0017] Elements in the figures are illustration and may not have been drawn to scale.
[0018] Figure 1 illustrates a layout of a direct reduction plant allowing to perform a method according to the invention. The direct reduction furnace (or shaft) 1 is charged at its top with oxidized iron 10 in form of ore or pellets. Said iron 10 is reduced into the furnace 1 by a reducing gas 11 injected into the furnace and flowing counter-current from oxidized iron. Reduced iron 12 exits the bottom of the furnace 1 for further processing, such as briquetting before being used in subsequent steelmaking steps. Reducing gas after having reduced iron exits at the top of the furnace as a top reduction gas 20 (TRG).
[0019] The top reduction gas 20 usually comprises from 15 to 25%v of CO, from 12 to 20%v of C02, from 35 to 55% of H2, from 15 to 25%v of H20, from 1 to 4% of N2. It has a temperature from 250 to 500°C.
[0020] A cooling gas 13 is captured out of the cooling zone of the furnace, subjected to a cleaning step into a cleaning device 30, such as a scrubber, compressed in a compressor 31 and then sent back to the cooling zone of the shaft 1.
[0021 ] According to the invention, the top reduction gas 20, preferentially after a dust and mist removal step in a cleaning device 5, such as a scrubber and a demister, is sent to a C02 recovery device 8 where C02 from the top reduction gas is concentrated and divided into a C02-poor stream 21 and a C02-rich stream 22. The first stream 21 , being poor in C02, is sent to a preparation device 7 where it will be mixed with other gas, optionally reformed and heated to produce the reducing gas 11. In a preferred embodiment, the preparation device 7 is a reformer. The preparation device 7 emits a preparation exhaust gas 27, also called stack gas. [0022] The C02 recovery device may be an absorption device, an adsorption device, a cryogenic distillation device or membranes. It could also be a combination of those different devices.
[0023] The second stream 22, which is rich in C02 and representing preferably from 1 to 20%v of the top reduction gas 20, is sent to a hydrocarbon production device 6 to be subjected to a hydrocarbon production step. This second stream may comprise between 80 and 100%v of C02. In the hydrocarbon production device 6, C02 is first transformed into carbon monoxide CO. This may be done for example through a hydrogenation step, when hydrogen is available in sufficient amount, to produce CO according to the following reaction: C02 + H2 -> CO + H20
This reaction is the so-called Reverse Water Gas Shift reaction (RGWS). This reaction is performed in presence of a catalyst such as ZnAI204 or Fe203/Cr203. It may also be done by a thermochemical transformation such as Boudouard Reaction or methane reforming, by an electrochemical transformation or with a plasma technology.
[0024] CO thus produced in then transformed into hydrocarbons according to Fischer-Tropsch reactions:
(2n+1)H2 + nCO -> CnH n+2 + nH20
Wherein n is an integer superior or equal to land is preferentially from 1 to 5. The man skilled in the art know how to choose the right catalyst and process conditions to perform the wanted Fischer-Tropsch reaction and produce the targeted hydrocarbon.
[0025] In a preferred embodiment C02 and H2 contained into the C02-rich stream 22 react to form methane CFI4 according to the following reaction: C02 + 4 H2 -> CH4 + 2H20
[0026] In this embodiment the hydrocarbon production device is a methanation device 6 such as catalytic reactors, bioreactors, cold plasma/DBD reactors or warm plasma reactors.
[0027] In case the content of H2 into the top reduction gas and thus in the second stream 22 would not be enough for the hydrocarbon production reaction, additional H2 stream 40 may be supplied to the hydrocarbon production unit 6. This H2 stream may be provided by a dedicated H2 production plant 9, such as an electrolysis plant. It may be a water or steam electrolysis plant. It is preferably operated using CO2 neutral electricity which includes notably electricity from renewable source which is defined as energy that is collected from renewable resources, which are naturally replenished on a human timescale, including sources like sunlight, wind, rain, tides, waves, and geothermal heat. In some embodiments, the use of electricity coming from nuclear sources can be used as it is not emitting CO2 to be produced.
[0028] This H2 stream 40 may also be added to the reducing gas 11. [0029] The stack gas 27 may also be supplied to the hydrocarbon production unit 6.
[0030] In a preferred embodiment, the hydrocarbon product 23 exiting the hydrocarbon production device 6 is reinjected into the furnace 1.
[0031] In a first embodiment, illustrated by stream 24, this hydrocarbon product 23 is a gas which is mixed with the reducing gas in the preparation device.
[0032] In a second embodiment, illustrated by stream 25, it is either injected into the furnace together with the reducing gas or injected independently in the transition zone of the furnace. In a third embodiment, illustrated by stream 26, it is either injected into the furnace together with the cooling gas 13 or injected independently in the cooling zone of the furnace. The hydrocarbon product 23 may be in a gaseous and/or in a liquid form. All those embodiments may be combined with one another.
[0033] In all embodiments, the hydrocarbon product serves as a carbon supplier for the DRI product. In a preferred embodiment, carbon content of the Direct Reduced Iron is set from 0.5 to 3 wt.%, preferably from 1 to 2 wt.% which allows getting a Direct Reduced Iron that can be easily handled and that keeps a good combustion potential for its future use. The amount of gas sent to the hydrocarbon production device may be controlled according to the amount of carbon needed in the DRI product.
[0034] The method according to the invention allows to reduce the carbon footprint of the direct reduction process by capture and use of the emitted C02. It may also avoid the need of an external source to increase the carbon content into the DRI product.
Claims
1) A method for manufacturing direct reduced iron wherein iron ore is reduced in a direct reduction furnace by a reducing gas, said reducing gas exiting said furnace through the top as a top reduction gas, said top reduction gas being captured and at least partly subjected to a C02 recovery step during which it is divided into two streams, a C02-rich stream and a C02-poor stream, said C02-rich stream being subjected to an hydrocarbon production step to produce an hydrocarbon product.
2) A method according to claim 1 wherein said hydrocarbon product is then at least partly injected into the direct reduction furnace.
3) A method according to claim 1 wherein the C02-poor stream is re-injected into the furnace as reducing gas.
4) A method according to claim 1 or 2 wherein the C02-rich stream contains between 80 and 100% in volume of carbon dioxide. 5) A method according to anyone of the previous claims wherein from 1 to 20% in volume of said top reduction gas is subjected to the hydrocarbon production step.
6) A method according to anyone of the previous claims wherein a hydrogen stream is supplied to the hydrocarbon production step to react with the C02-rich stream.
7) A method according to anyone of the previous claims wherein the produced hydrocarbon product is a gas which is mixed with the reduction gas before its injection into the furnace.
8) A method according to anyone of the previous claims wherein the produced hydrocarbon is a liquid.
9) A method according to anyone of the previous claims wherein the produced hydrocarbon is injected separately from the reducing gas, in the transition zone of the furnace.
10) A method according to anyone of the previous claims wherein the produced hydrocarbon is injected in the cooling zone of the furnace.
11) A method according to anyone of the previous claims wherein the hydrocarbon chain includes from 1 to 5 carbons. 12) A method according to anyone of the previous claims wherein the hydrocarbon production step is a methanation step.
13) A method according to claim 11 wherein the methanation step is a cold plasma reaction.
14) A method according to anyone of the previous claims wherein, prior to its injection into the direct reduction furnace, the reducing gas is heated in a reducing gas preparation step, said reducing gas preparation step emitting a preparation exhaust gas which is at least partly supplied to the hydrocarbon production step.
15) Direct reduction plant to perform a method according to anyone of the previous claims, said direct reduction plant comprising a hydrocarbon production unit.
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CN202190001036.5U CN221166600U (en) | 2021-05-31 | 2021-05-31 | Direct reduction facility for manufacturing direct reduced iron |
PCT/IB2021/054755 WO2022254235A1 (en) | 2021-05-31 | 2021-05-31 | A method for manufacturing direct reduced iron |
DE112021007754.6T DE112021007754T5 (en) | 2021-05-31 | 2021-05-31 | Process for the production of directly reduced iron |
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WO2024127074A1 (en) * | 2022-12-16 | 2024-06-20 | Arcelormittal | Method for manufacturing direct reduced iron with a low carbon content |
Citations (4)
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EP2543743A1 (en) * | 2010-03-02 | 2013-01-09 | JFE Steel Corporation | Blast furnace operation method, iron mill operation method, and method for utilizing a gas containing carbon oxides |
EP3156519A1 (en) * | 2015-10-16 | 2017-04-19 | Volkswagen Aktiengesellschaft | Method and appartus for producing a hydrocarbon |
DE102016008915A1 (en) * | 2016-07-21 | 2018-01-25 | Helmut Aaslepp | CO2 emission-free blast furnace process |
US20180178292A1 (en) * | 2016-12-22 | 2018-06-28 | Pioneer Astronautics | Novel Methods of Metals Processing |
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2021
- 2021-05-31 WO PCT/IB2021/054755 patent/WO2022254235A1/en active Application Filing
- 2021-05-31 DE DE112021007754.6T patent/DE112021007754T5/en active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
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EP2543743A1 (en) * | 2010-03-02 | 2013-01-09 | JFE Steel Corporation | Blast furnace operation method, iron mill operation method, and method for utilizing a gas containing carbon oxides |
EP3156519A1 (en) * | 2015-10-16 | 2017-04-19 | Volkswagen Aktiengesellschaft | Method and appartus for producing a hydrocarbon |
DE102016008915A1 (en) * | 2016-07-21 | 2018-01-25 | Helmut Aaslepp | CO2 emission-free blast furnace process |
US20180178292A1 (en) * | 2016-12-22 | 2018-06-28 | Pioneer Astronautics | Novel Methods of Metals Processing |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2024127074A1 (en) * | 2022-12-16 | 2024-06-20 | Arcelormittal | Method for manufacturing direct reduced iron with a low carbon content |
WO2024127360A1 (en) * | 2022-12-16 | 2024-06-20 | Arcelormittal | Method for manufacturing direct reduced iron with a low carbon content |
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