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WO2025147195A1 - Procédé de mesure du taux de conversion dans un processus de réduction - Google Patents

Procédé de mesure du taux de conversion dans un processus de réduction Download PDF

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Publication number
WO2025147195A1
WO2025147195A1 PCT/NL2025/050006 NL2025050006W WO2025147195A1 WO 2025147195 A1 WO2025147195 A1 WO 2025147195A1 NL 2025050006 W NL2025050006 W NL 2025050006W WO 2025147195 A1 WO2025147195 A1 WO 2025147195A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
reduction
conversion
measured
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/NL2025/050006
Other languages
English (en)
Inventor
Jurre VAN MEEL
Lex SCHEEPERS
Vincent Jacobus Theodorus SEIJGER
Jeroen Gabriël Franciscus HOUTAPPELS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Renewable Iron Fuel Technology BV
Original Assignee
Renewable Iron Fuel Technology BV
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 Technology BV filed Critical Renewable Iron Fuel Technology BV
Publication of WO2025147195A1 publication Critical patent/WO2025147195A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/001—Injecting additional fuel or reducing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/24—Test rods or other checking devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B1/00—Shaft or like vertical or substantially vertical furnaces
    • F27B1/10—Details, accessories or equipment specially adapted for furnaces of these types
    • F27B1/28—Arrangements of monitoring devices, of indicators, of alarm devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D21/00—Arrangement of monitoring devices; Arrangement of safety devices
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/001—Injecting additional fuel or reducing agents
    • C21B2005/005—Selection or treatment of the reducing gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F27D2019/0006—Monitoring the characteristics (composition, quantities, temperature, pressure) of at least one of the gases of the kiln atmosphere and using it as a controlling value
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F27D2019/0006—Monitoring the characteristics (composition, quantities, temperature, pressure) of at least one of the gases of the kiln atmosphere and using it as a controlling value
    • F27D2019/0012—Monitoring the composition of the atmosphere or of one of their components
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D21/00—Arrangement of monitoring devices; Arrangement of safety devices
    • F27D2021/0007—Monitoring the pressure

Definitions

  • the present invention relates to a method for measuring the rate of conversion in a reduction process.
  • the present invention also relates to the use of the rate of conversion measured in a reduction process for adjusting operating conditions in the reactor.
  • 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.
  • 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.
  • US 5,366,897 discloses a process for converting iron-containing feed to a product comprising iron carbide, the process comprising the steps of inputting to a reactor an iron-containing reactor feed; contacting said reactor feed in said reactor with a gas mixture comprising a reducing gas and a carburizing gas; evaluating whether the rate of conversion of reactor feed into iron carbide is acceptable; and adjusting as necessary reactor pressure to convert reactor feed into iron carbide at an acceptable rate; and converting at least a portion of said reactor feed to iron carbide at an acceptable rate.
  • Such process further comprises the steps of generating a phase stability diagram for conditions of temperature, pressure and gas compositions in the reactor, determining from said phase stability diagram whether conditions of temperature, pressure and gas concentrations in the reactor are suitable for converting reactor feed into iron carbide, and adjusting as necessary at least one parameter selected from the group consisting of reactor temperature, reactor pressure, and gas compositions in the reactor to convert reactor feed into iron carbide.
  • spectroscopy such as mass spectrometry (MS) and X-ray fluorescence (XRF), thermogravimetric analysis (TGA), X-ray diffraction (XRD), electrical resistance measurements, microscopy techniques, and load cells, i.e. weight measurements.
  • MS mass spectrometry
  • XRF X-ray fluorescence
  • TGA thermogravimetric analysis
  • XRD X-ray diffraction
  • electrical resistance measurements i.e. weight measurements.
  • microscopy techniques i.e. weight measurements.
  • the reduction gas further comprises carbon monoxide.
  • Syngas synthesis gas
  • the reduction gas comprises carbon monoxide as well
  • a sensor for measuring the carbon monoxide content in the reduction gas entering the reactor and a sensor for measuring the carbon dioxide content in the exhaust gas leaving the reactor are needed for accurately measuring the conversion of iron oxide powder towards powder comprising iron.
  • carbon monoxide is converted into carbon dioxide via CO + FeO -> CO 2 + Fe.
  • the present method can be described via the reaction equation of the reduction of iron oxide, wherein iron oxide may be present as a mixture of for example FeO, Fe2O3 and Fe3O4: F e ⁇ O ⁇ + 3H ⁇ ⁇ 2Fe + 3H ⁇ O Fe3O4 + 4H2 ⁇ 3 Fe + 4 H2O FeO + H2 ⁇ Fe + H2O Or in more general terms: FexOy + yH2 ⁇ xFe + yH2O
  • iron oxide powder is contacted with a reduction gas in a reactor and converted into powder comprising iron and an exhaust gas, according to reaction equation.
  • an additional humidity transmitter positioned upstream of the reactor can be used for making a correction for the actual formed water measured by the humidity transmitter positioned downstream of the reactor.
  • a small amount of H 2 O will enter the reactor since in practice separation of H 2 O and H 2 is not 100% perfect and thus a compensation must be carried out, i.e. subtracting that amount from the amount measured at the exhaust.
  • the present method also enables the ability to make conversion plots over time.
  • the mass flow is also measured.
  • the amount of oxygen ⁇ ⁇ ⁇ ⁇ ⁇ , ⁇ that has reacted in the reactor i.e. the mass flow
  • M is the molar mass in kg/mol:
  • the maximum oxygen uptake ( ⁇ ⁇ ⁇ , ⁇ ) can be determined:
  • the solids conversion ⁇ is given by: In the present method for measuring the rate of conversion in a reduction process, such as an iron oxide powder reduction process additional measurements of pressure, temperature and mass flow of the inlet stream of reduction gas in the reactor and the outlet stream of water-containing gas from the reactor are carried out.
  • the values obtained may be used in the calculation of the solids conversion ⁇ . It is to be noted that the present inventors found that in a commercial reduction process more H 2 is used than theoretically needed to convert all Fe 2 O 3 and Fe 3 O 4 into Fe.
  • a schematic overview of a reduction process such as an iron oxide powder reduction process can be found in the enclosed Figure.
  • the iron oxide powder 2 is contacted with a reduction gas 1 in a reactor 5 and converted into powder comprising iron 3 and an exhaust gas 4.
  • the reduction gas 1 entering the reactor 5 is monitored for several process parameters, such as percentage hydrogen 10, percentage humidity 11, temperature 12, pressure 13 and mass flow 14.
  • the exhaust gas 4 leaving the reactor 5 is also monitored for several process parameters, such as percentage humidity 16, temperature 17 and pressure 18.
  • the mass flow of iron oxide powder 2 entering the reactor 5 is measured via a weight transmitter 15 as well.
  • sensors 10-18 for each process parameters are shown but in practice a sensor can be used for measuring a combination of several parameters.
  • a hydrogen sensor can be used for measuring not only hydrogen but pressure, temperature and humidity as well.
  • Exhaust gas 4 is further processed in downstream equipment (not shown here).
  • An example of process control is as follows. The process operator measures during a steady state situation that the desired conversion rate is not achieved. The process operator may take action to increase the conversion rate. For example, the process operator increases the temperature of the reactor. Such an increase will lead to a faster reaction which is advantageous from both a kinetic and a thermodynamic point of view. For example, the process operator may also increase the pressure of the reactor.
  • the process operator may also increase the mass flow of the reduction gas.
  • Such an increase may change the fluidization regime in the fluidized bed, e.g. from a bubbling regime to a turbulent regime, resulting in a better mass transfer between gas and iron oxide particle.
  • the excess amount of hydrogen will be greater and therefore also the hydrogen recycle (which in turn is less efficient for energy management).
  • a low mass flow of hydrogen is more efficient for the hydrogen conversion and therefore the hydrogen recycling. Such a situation can be seen as an economic consideration where an optimum can be found.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Compounds Of Iron (AREA)

Abstract

La présente invention concerne un procédé de mesure du taux de conversion dans un processus de réduction, un oxyde métallique contenant des matériaux de charge, tels que de la poudre d'oxyde de fer, étant mis en contact avec un gaz de réduction dans un réacteur et converti en poudre comprenant du fer et un gaz d'échappement. La présente invention concerne également l'utilisation du taux de conversion mesuré dans un tel processus de réduction pour ajuster les conditions de fonctionnement dans le réacteur.
PCT/NL2025/050006 2024-01-03 2025-01-03 Procédé de mesure du taux de conversion dans un processus de réduction Pending WO2025147195A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2036729 2024-01-03
NL2036729A NL2036729B1 (en) 2024-01-03 2024-01-03 method for measuring the rate of conversion in a reduction process

Publications (1)

Publication Number Publication Date
WO2025147195A1 true WO2025147195A1 (fr) 2025-07-10

Family

ID=89767178

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2025/050006 Pending WO2025147195A1 (fr) 2024-01-03 2025-01-03 Procédé de mesure du taux de conversion dans un processus de réduction

Country Status (2)

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NL (1) NL2036729B1 (fr)
WO (1) WO2025147195A1 (fr)

Citations (9)

* 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
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
US5366897A (en) 1990-08-01 1994-11-22 Iron Carbide Holdings, Ltd. Method for controlling the conversion of iron-containing reactor feed into iron carbide
WO2000001856A1 (fr) 1998-07-06 2000-01-13 Hylsa, S.A. De C.V. Procede et appareil de reduction des particules d'oxydes de fer dont la taille est comprise dans une grande plage de tailles
US20160348199A1 (en) 2014-02-10 2016-12-01 Primetals Technologies Austria GmbH Pneumatic ore charging
US20220162076A1 (en) 2020-11-20 2022-05-26 Carbon Technology Holdings, LLC Biomass pyrolysis integrated with bio-reduction of metal ores, hydrogen production, and/or activated-carbon production
WO2023121465A1 (fr) 2021-12-24 2023-06-29 Renewable Iron Fuel Technology B.V. Procédé de production de carburant à base de fer.

Patent Citations (9)

* 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
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
US5366897A (en) 1990-08-01 1994-11-22 Iron Carbide Holdings, Ltd. Method for controlling the conversion of iron-containing reactor feed into iron carbide
WO2000001856A1 (fr) 1998-07-06 2000-01-13 Hylsa, S.A. De C.V. Procede et appareil de reduction des particules d'oxydes de fer dont la taille est comprise dans une grande plage de tailles
US20160348199A1 (en) 2014-02-10 2016-12-01 Primetals Technologies Austria GmbH Pneumatic ore charging
US20220162076A1 (en) 2020-11-20 2022-05-26 Carbon Technology Holdings, LLC Biomass pyrolysis integrated with bio-reduction of metal ores, hydrogen production, and/or activated-carbon production
WO2023121465A1 (fr) 2021-12-24 2023-06-29 Renewable Iron Fuel Technology B.V. Procédé de production de carburant à base de fer.

Also Published As

Publication number Publication date
NL2036729B1 (en) 2025-07-18

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