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NL2036812B1 - A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials - Google Patents

A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials

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Publication number
NL2036812B1
NL2036812B1 NL2036812A NL2036812A NL2036812B1 NL 2036812 B1 NL2036812 B1 NL 2036812B1 NL 2036812 A NL2036812 A NL 2036812A NL 2036812 A NL2036812 A NL 2036812A NL 2036812 B1 NL2036812 B1 NL 2036812B1
Authority
NL
Netherlands
Prior art keywords
metal oxide
charge materials
reactor
containing charge
oxide containing
Prior art date
Application number
NL2036812A
Other languages
Dutch (nl)
Inventor
Van Meel Jurre
Scheepers Lex
Gabriël Franciscus Houtappels Jeroen
Original Assignee
Renewable Iron Fuel Tech B V
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Renewable Iron Fuel Tech B V filed Critical Renewable Iron Fuel Tech B V
Priority to NL2036812A priority Critical patent/NL2036812B1/en
Priority to PCT/NL2025/050010 priority patent/WO2025155189A1/en
Application granted granted Critical
Publication of NL2036812B1 publication Critical patent/NL2036812B1/en

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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
    • C21B13/0033—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
    • C21B13/0073—Selection or treatment of the reducing gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0086—Conditioning, transformation of reduced iron ores
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • C21B13/146—Multi-step reduction without melting
    • 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
    • C21B2100/66—Heat exchange
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Iron (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

The present invention relates to a method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials, the method comprising a step of feeding metal oxide containing charge materials to a reactor, a step of reducing the metal oxide containing charge materials by flowing a reduction gas through the reactor, a step of removing partially spent reduction gas from the reactor, and a step of removing a stream containing iron fuel from the reactor.

Description

Title: A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials
Description:
The present invention relates to a method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials.
A reduction process, such as an iron oxide powder reduction process, is known from WO 2023/121465 in the name of the present applicants. According to such method the metal oxide containing charge materials is fed to a fluidized bed unit, wherein the metal oxide containing charge materials is reduced by flowing a reduction gas through the fluidized bed unit, wherein the fluidized bed unit is operated under specific reduction conditions. Partially spent reduction gas is removed from the fluidized bed unit and admixed with fresh reduction gas and the mixture of partially spent reduction gas and fresh reduction gas is returned to the fluidized bed unit. A stream containing iron fuel is continuously removed from the fluidized bed unit. Such method for producing iron fuel further comprises pre-heating and/or drying the metal oxide containing charge materials before feeding the materials into the fluidized bed unit, wherein the pre-heating temperature is preferably in a range of 40 and 1000 °C.
No details about the specific way of pre-heating or heat integration has been disclosed in WO 2023/121465.
Other processes for reducing metal oxide containing charge materials are known from, inter alia, US 2016/348199, US 4,082,545, US 3,288,590, US 4,420,332,
WO 00/01856, and US 3,303,017.
Energy consumption in commercial plants plays a big role in the overall costs of operating a plant. In addition, the energy consumption should be reduced where possible, especially with regard to the emissions of harmful substances such as CO: and NO, to the environment.
An object of the present invention is to provide a method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials, in which method heat integration of several product streams takes place.
Another object of the present invention is to provide a method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials, in which method measurements are applied for maintaining stable reactor conditions.
The present invention thus relates to a method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials, the method comprising a step of feeding metal oxide containing charge materials to a reactor, a step of reducing the metal oxide containing charge materials by flowing a reduction gas through the reactor, a step of removing partially spent reduction gas from the reactor, and a step of removing a stream containing iron fuel from the reactor, wherein the stream containing iron fuel removed from the reactor is sent to a heat exchanger, wherein the heat extracted from the stream containing iron fuel is used to heat the metal oxide containing charge materials.
The present inventors found that by such a method one or more of the objects are achieved. The principle of the present method is based on heat integration of the solids, i.e. metal oxide containing charge materials, in an iron fuel production plant such that the energy efficiency of the plant is increased, and the product quality of the produced iron powder is improved.
In an iron fuel production plant iron oxide powder reacts with a reduction gas, e.g. gaseous hydrogen, in a reactor such that iron powder is produced. This process takes place in a reactor at high temperature. This reduction reaction is an endothermic reaction which means that energy is needed for the reaction, thereby reducing the temperature in the reactor. When solids having a low temperature are introduced into the reactor, this has to be compensated for by increasing the gas inlet temperature, or alternatively by heating the reactor walls, such that the reactor remains at the operating temperature.
The present inventors found that it is important to keep the temperature in the reactor as uniform and constant as possible. One of the reasons is that when the reactor temperature is too high this may result in agglomeration of the powder, potentially causing defluidization and blockage of the process. A uniform reactor temperature will produce powder by the same reaction mechanism, which will result in a final product having uniform final properties, for example particle porosity, pore size,
e.g. specific surface area and composition. A more uniform distribution of the specific surface area means a more constant and predictable ignition temperature which can be beneficial for the combustion plant and for process safety.
On the other hand, a reactor temperature that is too low may result in the formation of pyrophoric powder. Both particle agglomeration and the formation of pyrophoric material form a barrier for the use of iron in a specific powder form as a starting material in iron fuel combustion. The term “pyrophoricity” is to be understood as a property of a material. In more detail, a material is qualified as pyrophoric if it ignites spontaneously in air at or below 54 °C or within 5 minutes after coming into contact with air. It is caused by the high specific surface area of the material, yielding an extremely low ignition temperature for oxidation. When the ignition temperature is low enough, auto-ignition at atmospheric conditions can take place. Pyrophoricity of iron particles after reduction has been reported to be a serious issue in fluidized bed reduction, where a high surface area of the material is obtained. The tendency to reoxidation depends on the reduction temperature. Studies have shown that the surface area of fine metal powders generally decreases with higher reduction temperature.
In an example the metal oxide containing charge materials are first heated with the heat extracted from the stream containing iron fuel, and the thus preheated metal oxide containing charge materials are further heated by mixing the metal oxide containing charge materials with partially spent reduction gas removed from the reactor. In such an example the combination of two relatively hot process streams is used for heat integration, i.e. a stream of solids, namely the heat extracted from the stream containing iron fuel, and a stream of gas, namely the partially spent reduction gas removed from the reactor.
In an example the step of feeding metal oxide containing charge materials to the reactor comprises adding a gaseous mixture containing the metal oxide containing charge materials to a separation unit, said separation unit having an inlet for solids and gas, an outlet for solids and an outlet for gas, wherein the outlet for solids is connected to the reactor.
In an example of the present method the separation unit is a cyclone or a series of cyclones. A cyclone provides an intense interaction between solids and gas and is therefore very efficient in heat transfer processes. In addition, cyclones have simple designs, leading to lower maintenance requirements and are generally cost-effective due to their simplicity and effectiveness in heat transfer processes. In a cyclone there is a gas-solid interaction because the gas containing solid particles enters tangentially, creating a high-speed rotating airflow within the cyclone chamber. Another aspect of a cyclone is the centrifugal force, wherein due to the centrifugal force generated by the cyclone's rotation, solid particles move towards the outer wall, experiencing greater force than the gas molecules. In addition, two heat transfer mechanisms play a big role in the cyclone, i.e. convection and radiation. The high-speed gas flow around the solids leads to convective heat transfer. As the gas moves rapidly, it carries heat energy, which can be transferred to the solid particles. Depending on the temperature difference between the gas and solid particles, radiation heat transfer might occur. Hot gas can radiate heat energy to the cooler solid surfaces within the cyclone.
In an example the gaseous mixture containing the metal oxide containing charge materials is obtained by mixing the metal oxide containing charge materials with partially spent reduction gas removed from the reactor, wherein the mixture thus obtained is added to the cyclone or the series of cyclones via the inlet for solids and gas. In such a situation an optimal heat integration is carried out in which the relatively hot partially spent reduction gas is used as a heat transfer medium for the solids, i.e. the metal oxide containing charge materials. In addition, the relatively hot partially spent reduction gas removed from the reactor may contain solid material and this solid material will be returned to the reactor via the outlet for solids of the cyclone.
According to the present method the stream containing iron fuel removed from the reactor is sent to a heat exchanger, wherein the heat extracted from the stream containing iron fuel is used to heat the metal oxide containing charge materials. In such an example another relatively hot stream, i.e. stream containing iron fuel removed from the reactor, is used as a source of energy for heating the metal oxide containing charge materials.
In an example of the present invention the reactor is a fluidized bed unit, or a combination of fluidized bed units.
In an example the outlet for solids of the cyclone or the series of cyclones is positioned in such a way that gas from the fluidized bed cannot flow back into the cyclone via that outlet, causing it to no longer work. This can be achieved by protruding the outlet for solids of the cyclone or the series of cyclones, also called standpipe, into the bed so that the powder column provides resistance, or by using a valve or nozzle in the standpipe.
In an example the outlet for solids of the cyclone or the series of cyclones is positioned just below the fluidizing surface of the fluidized bed unit thereby enabling a 5 smooth contact between the solids coming from the cyclone or the series of cyclones and the solids already present in a fluidisation condition in the fluidized bed unit. Such a contact minimizes a disturbance of the fluidisation conditions in the fluidized bed unit.
To ensure a more uniform reactor temperature it is thus desired to preheat the powder before it interacts with the introduced hydrogen gas. This can be done by a bulk solid heat exchanger (BSHE) and/or by heating the powder by a gas flow. Using a bulk solid heat exchanger has its limitations in the maximum powder temperature which can be achieved since that temperature is highly dependent on the specific heat transfer medium. As the powder needs to be cooled after extraction from the reactor for safety reasons and handling reasons, a bulk solid heat exchanger can also be used here. The extracted heat from such a bulk solid heat exchanger can be used to heat the solids at the inlet stream from the reactor. The present inventors found that this process of heat integration will however still not preheat the solids all the way up to the desired reactor temperature due to the difference in mass flow of the particles in and out and their specific heat capacity. Therefore a second preheating step is needed in which the solids are introduced into the outlet gas flow of the reactor after which the heat up even further.
A drawing schematically illustrate an example of a method according to the invention according to the invention. The present method is not restricted to the specific example disclosed here.
Figure 1 is an example of the method for producing iron fuel.
A stream of metal oxide containing charge materials 12 is sent to a heat exchanger 11. A heated stream of metal oxide containing charge materials 10 is sent a mass flow device 9 and forwarded as stream 5 to a separation unit 3, e.g. a cyclone.
Examples of such mass flow device are screw conveyors or feeders, pneumatic conveying systems, vibratory feeders, chutes, and hoppers, wherein screw conveyors or feeders are preferred. A partially spent reduction gas 4 from a reactor 7, such as a fluidized bed unit, is mixed with stream 5 and a mixed stream 6 is added to the separation unit 3. In separation unit 3 a stream of further heated metal oxide containing charge materials 2 is added to reactor 7, such as a fluidized bed unit. In a situation wherein the temperature of metal oxide containing charge materials 2 is not at the right temperature for being added to reactor 7, such as a fluidized bed unit, an additional heating of stream 2 may be needed. Such an additional heating step may for example take place via conduction, in which the solids are passed through a heated surface or using heated plates to transfer heat directly. Or such an additional heating step may for example take place via indirect heat transfer in which heat is transferred to the solids without direct contact through a medium such as a jacketed tube, wherein a solid material passes through a tube surrounded by a heating jacket through which a heat transfer fluid flows, or even via radiant heating, wherein a radiant heat source (infrared heaters) is used to heat solids as they pass through or beneath.
Separation unit 3 also produces a gas stream 1, which can be used for further processing. A stream 15 containing iron fuel is removed from reactor 7, such as a fluidized bed unit, and forwarded to heat exchanger 16. Heat exchanger 16 is connected to heat exchanger 11 via a circuit of a heat transfer medium. A relatively hot stream 13 of heat transfer medium flows from heat exchanger 16 to heat exchanger 11, and a relatively cold stream 14 of heat transfer medium flows back from heat exchanger 11 to heat exchanger 16. According to such a circuit of heat transfer medium the heat extracted from stream 15 containing iron fuel is used to heat the metal oxide containing charge materials 12.
Although the Figure shows only one cyclone as separation unit, the present invention is not restricted to a single cyclone construction. A series of cyclones, placed in series or even parallel, or a combination thereof, can be used as well in the present method. The same applies to the fluidized bed unit which may consist of multiple fluidized bed units, placed in series or even parallel, or a combination thereof. A similar construction may be present for the heat exchanger, mass flow device, i.e. multiple units placed in series or even parallel, or a combination thereof.
In an example multiple reactors placed in series are connected to the same separation unit. In another example multiple reactors placed in parallel are connected to the same separation unit. In another example one or more separation units are connected to multiple reactors placed in series.

Claims (7)

CONCLUSIESCONCLUSIONS 1. Werkwijze voor het produceren van ijzerbrandstof uit metaaloxide bevattende ladingsmaterialen via het reduceren van de metaaloxide bevattende ladingsmaterialen, waarbij de werkwijze een stap omvat van het toevoeren van metaaloxide bevattende ladingsmaterialen aan een reactor, een stap van het reduceren van de metaaloxide bevattende ladingsmaterialen door het laten stromen van een reductiegas door de reactor, een stap van het verwijderen van gedeeltelijk verbruikt reductiegas uit de reactor, en een stap van het uit de reactor verwijderen van een stroom die ijzerbrandstof bevat, waarbij de ijzerbrandstof bevattende stroom, die uit de reactor wordt verwijderd, naar een warmtewisselaar wordt geleid, waarbij de warmte onttrokken aan de jzerbrandstof bevattende stroom wordt toegepast om de metaaloxide bevattende ladingsmaterialen te verwarmen.A method for producing iron fuel from metal oxide-containing charge materials by reducing the metal oxide-containing charge materials, the method comprising a step of feeding metal oxide-containing charge materials to a reactor, a step of reducing the metal oxide-containing charge materials by flowing a reducing gas through the reactor, a step of removing partially spent reducing gas from the reactor, and a step of removing a stream containing iron fuel from the reactor, wherein the iron fuel-containing stream removed from the reactor is passed to a heat exchanger, wherein the heat extracted from the iron fuel-containing stream is used to heat the metal oxide-containing charge materials. 2. Werkwijze volgens conclusie 1, waarbij de metaaloxide bevattende ladingsmaterialen eerst worden verwarmd met de warmte onttrokken aan de jzerbrandstof bevattende stroom, en de aldus voorverwarmde metaaloxide bevattende ladingsmaterialen verder worden verwarmd door het mengen van de metaaloxide bevattende ladingsmaterialen met gedeeltelijk verbruikt reductiegas dat uit de reactor is verwijderd.2. The method of claim 1, wherein the metal oxide-containing charge materials are first heated with the heat extracted from the iron fuel-containing stream, and the thus preheated metal oxide-containing charge materials are further heated by mixing the metal oxide-containing charge materials with partially spent reducing gas removed from the reactor. 3. Werkwijze volgens een of meer van de conclusies 1-2, waarbij de stap van het toevoeren van metaaloxide-bevattende ladingsmaterialen aan de reactor omvat het aan een scheidingseenheid toevoeren van een gasvormig mengsel dat de metaaloxide-bevattende ladingsmaterialen bevat, waarbij genoemde scheidingseenheid is voorzien van een inlaat voor vaste stoffen en gas, een uitlaat voor vaste stoffen en een uitlaat voor gas, waarbij de uitlaat voor vaste stoffen is verbonden met de reactor.A method according to any one of claims 1 to 2, wherein the step of feeding metal oxide-containing charge materials to the reactor comprises feeding a gaseous mixture containing the metal oxide-containing charge materials to a separation unit, said separation unit having a solids and gas inlet, a solids outlet and a gas outlet, the solids outlet being connected to the reactor. 4. Werkwijze volgens conclusie 3, waarbij de scheidingseenheid een cycloon of een reeks cyclonen is.A method according to claim 3, wherein the separation unit is a cyclone or a series of cyclones. 5. Werkwijze volgens een of meer van de conclusies 3-4, waarbij het gasmengsel, dat de metaaloxide bevattende ladingsmaterialen bevat, wordt verkregen door het mengen van de metaaloxide bevattende ladingsmaterialen met gedeeltelijk verbruikt reductiegas dat uit de reactor is verwijderd, waarbij het aldus verkregen mengsel via de inlaat voor vaste stoffen en gas aan de cycloon of de reeks cyclonen wordt toegevoegd.5. A method according to any one of claims 3 to 4, wherein the gas mixture containing the metal oxide-containing charge materials is obtained by mixing the metal oxide-containing charge materials with partially spent reducing gas removed from the reactor, the mixture so obtained being introduced into the cyclone or bank of cyclones via the solids and gas inlet. 6. Werkwijze volgens een of meer van de voorgaande conclusies, waarbij de reactor een wervelbedeenheid is.6. A method according to any preceding claim, wherein the reactor is a fluidised bed unit. 7. Werkwijze volgens conclusie 6, waarbij de uitlaat voor vaste stoffen van de cycloon of de reeks cyclonen net onder het fluïdisatieoppervlak van de wervelbedeenheid wordt gepositioneerd.7. A method as claimed in claim 6, wherein the solids outlet of the cyclone or series of cyclones is positioned just below the fluidising surface of the fluidised bed unit.
NL2036812A 2024-01-16 2024-01-16 A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials NL2036812B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NL2036812A NL2036812B1 (en) 2024-01-16 2024-01-16 A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials
PCT/NL2025/050010 WO2025155189A1 (en) 2024-01-16 2025-01-06 A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials

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NL2036812A NL2036812B1 (en) 2024-01-16 2024-01-16 A method for producing iron fuel from metal oxide containing charge materials via reducing the metal oxide containing charge materials

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288590A (en) 1963-07-22 1966-11-29 Hydrocarbon Research Inc Continuous oxide reduction process
US3303017A (en) 1963-11-14 1967-02-07 Exxon Research Engineering Co Metal treating process
US4082545A (en) 1975-08-05 1978-04-04 Istituto Di Ricerca Finsider Per La Riduzione Diretta S.P.A. Reduction of iron ore in fluidized bed reactors
GB1506170A (en) * 1974-03-08 1978-04-05 Stora Kopparbergs Bergslags Ab Process and apparatus for reducing pulverized material containing iron oxides
US4420332A (en) 1980-12-22 1983-12-13 Research Association For Residual Oil Processing Process for the production of reduced iron and thermal cracking of heavy oils
US5431711A (en) * 1994-08-12 1995-07-11 Midrex International B.V. Rotterdam, Zurich Branch Circulating fluidized bed direct reduction system
US5527379A (en) * 1993-06-19 1996-06-18 Metallgesellschaft Aktiengesellschaft Process for a direct reduction of iron oxide containing materials to form Fe3 C
WO2000001856A1 (en) 1998-07-06 2000-01-13 Hylsa, S.A. De C.V. Method and apparatus for reducing iron-oxides-particles having a broad range of sizes
US20160348199A1 (en) 2014-02-10 2016-12-01 Primetals Technologies Austria GmbH Pneumatic ore charging
WO2023121465A1 (en) 2021-12-24 2023-06-29 Renewable Iron Fuel Technology B.V. A method for producing iron fuel

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288590A (en) 1963-07-22 1966-11-29 Hydrocarbon Research Inc Continuous oxide reduction process
US3303017A (en) 1963-11-14 1967-02-07 Exxon Research Engineering Co Metal treating process
GB1506170A (en) * 1974-03-08 1978-04-05 Stora Kopparbergs Bergslags Ab Process and apparatus for reducing pulverized material containing iron oxides
US4082545A (en) 1975-08-05 1978-04-04 Istituto Di Ricerca Finsider Per La Riduzione Diretta S.P.A. Reduction of iron ore in fluidized bed reactors
US4420332A (en) 1980-12-22 1983-12-13 Research Association For Residual Oil Processing Process for the production of reduced iron and thermal cracking of heavy oils
US5527379A (en) * 1993-06-19 1996-06-18 Metallgesellschaft Aktiengesellschaft Process for a direct reduction of iron oxide containing materials to form Fe3 C
US5431711A (en) * 1994-08-12 1995-07-11 Midrex International B.V. Rotterdam, Zurich Branch Circulating fluidized bed direct reduction system
WO2000001856A1 (en) 1998-07-06 2000-01-13 Hylsa, S.A. De C.V. Method and apparatus for reducing iron-oxides-particles having a broad range of sizes
US20160348199A1 (en) 2014-02-10 2016-12-01 Primetals Technologies Austria GmbH Pneumatic ore charging
WO2023121465A1 (en) 2021-12-24 2023-06-29 Renewable Iron Fuel Technology B.V. A method for producing iron fuel

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