WO2008020357A2 - A method for the commercial production of iron - Google Patents

A method for the commercial production of iron Download PDF

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Publication number
WO2008020357A2
WO2008020357A2 PCT/IB2007/053016 IB2007053016W WO2008020357A2 WO 2008020357 A2 WO2008020357 A2 WO 2008020357A2 IB 2007053016 W IB2007053016 W IB 2007053016W WO 2008020357 A2 WO2008020357 A2 WO 2008020357A2
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WO
WIPO (PCT)
Prior art keywords
reactor
containing material
iron
carbon
iron oxide
Prior art date
Application number
PCT/IB2007/053016
Other languages
French (fr)
Other versions
WO2008020357A3 (en
Inventor
Gerard Pretorius
Derek Roy Oldnall
Original Assignee
Iron Mineral Beneficiation Services (Proprietary) Limited
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
Priority to CA2659559A priority Critical patent/CA2659559C/en
Priority to BRPI0715117A priority patent/BRPI0715117B1/en
Priority to EP07825975A priority patent/EP2057294B1/en
Priority to DE602007014062T priority patent/DE602007014062D1/en
Priority to CN2007800309460A priority patent/CN101506390B/en
Priority to PL07825975T priority patent/PL2057294T3/en
Application filed by Iron Mineral Beneficiation Services (Proprietary) Limited filed Critical Iron Mineral Beneficiation Services (Proprietary) Limited
Priority to US12/375,760 priority patent/US8613787B2/en
Priority to AU2007285415A priority patent/AU2007285415B2/en
Priority to AT07825975T priority patent/ATE506457T1/en
Publication of WO2008020357A2 publication Critical patent/WO2008020357A2/en
Publication of WO2008020357A3 publication Critical patent/WO2008020357A3/en
Priority to US14/014,340 priority patent/US9150939B2/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/14Multi-stage processes processes carried out in different vessels or furnaces
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/004Making spongy iron or liquid steel, by direct processes in a continuous way by reduction from ores
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/08Making spongy iron or liquid steel, by direct processes in rotary furnaces
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/12Making spongy iron or liquid steel, by direct processes in electric furnaces
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B7/00Rotary-drum furnaces, i.e. horizontal or slightly inclined

Definitions

  • THIS INVENTION relates to a method for the commercial production of iron. It also relates to a reactor assembly and a vehicle for use in the commercial production of iron.
  • the charcoal acted both as the source of heat and as the reducing agent.
  • the product was an alloy consisting of about 96,5% iron and about 3,5% carbon. Charcoal was later supplanted by coke.
  • iron is produced largely from the iron ores haematite (Fe 2 Os) and magnetite (F ⁇ 3 ⁇ 4 ) by carbothermic reduction in a blast furnace at temperatures of about 2000 0 C.
  • the iron ore, carbon in the form of coke and a flux such as limestone are fed into the top of the furnace and a blast of heated air is forced into the bottom of the furnace.
  • the coke reacts with oxygen in the air blast to produce carbon monoxide and the carbon monoxide reduces the iron ore to iron, becoming oxidised to carbon dioxide in the process.
  • the iron produced in this process is called pig iron.
  • the iron oxide and coke have to be in relatively coarse particulate form, preferably with particle sizes larger than about 6mm. If the particle size is substantially less than 6mm, the feedstock will simply be blown out of the top of the blast furnace by the gas stream.
  • there are inherent problems associated with the operation of blast furnaces in preventing the formation of hot and cold zones which can result in back reactions and competing reactions.
  • Finely divided iron oxide is also produced as a by-product both in the production of copper, e.g. in the case of Phalaborwa Mining Corporation in South Africa or Freeport (Grasberg) in Indonesia and from the roasting of FeS 2 in the production of sulphuric acid.
  • These finely divided materials could provide a source of raw material for the production of iron.
  • these materials are first granulated, they cannot be used in blast furnaces, but granulation is not economically viable. It is an object of the invention to address this problem.
  • a method for the production of iron from an iron oxide-containing material including contacting an iron oxide-containing material with a particle size distribution range with a ⁇ 90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a ⁇ 90 of less than 6mm, in a commercial scale reactor at a temperature of between 900 ° C and 1200 ° C for a contact time sufficient to reduce the iron oxide to iron.
  • substantially all of the iron oxide-containing material is reduced to iron.
  • ⁇ 90 means that at least 90% of the material has a particle size less than that specified, i.e. a ⁇ 90 of 2mm means that at least 90% of the particulate material has a particle size of less than 2mm.
  • ⁇ 90 is also often simply written as d90.
  • commercial scale reactor is meant a reactor capable of routinely producing at least 1000 kg/h of iron.
  • the iron oxide-containing material may have a ⁇ 90 of less than 1 mm.
  • PPrreeffeerraabbllyy,, ttrhe iron oxide-containing material has a ⁇ 90 of less than 500 ⁇ m.
  • TThhee ccaarrbboonn--ccoonnttaaiinniinngg mmaatteerriiaall n may have a ⁇ 90 of less than 2mm.
  • the carbon-containing material has a ⁇ 90 of less than 1 mm.
  • the contact time may be between 30 minutes and 360 minutes.
  • the contact time is preferably between about 60 minutes and about 180 minutes and more preferably about 120 minutes.
  • the method may include contacting the iron oxide-containing material with the carbon-containing material in the presence of a flux such as calcium oxide or quicklime.
  • the iron oxide-containing material may be waste iron oxide. It may in particular be the waste product produced in the mining of iron ore, in the production of copper or in the production of sulphuric acid. This material typically has a particle size with a ⁇ 90 of less than about 500 ⁇ m and usually consists of haematite or magnetite.
  • the carbon-containing material may be waste coal or coal fines, often referred to as duff which is produced during the mining and transport of coal. Instead, the carbon- containing material may be the waste material produced in the distillation or devolatilisation of coal.
  • the carbon-containing material is preferably de-volatilised coal fines. This material typically has a particle size with a ⁇ 90 of less than about 6mm.
  • the temperature in the reactor may be between 1000 0 C and 1 100 0 C, e.g. about 1050°C.
  • the method may include heating the reactor using an external heat source.
  • the reactor is heated electrically.
  • CaCO 3 CaO + CO 2
  • FeSiO 3 and Fe 2 SiO 4 occurs from above 700 0 C and active CaO is needed to react with the SiO 2 before it combines with the FeO.
  • Contacting the iron oxide-containing material with the carbon-containing material may include feeding pre-determined quantities of said materials into a rotating cylindrical reactor or rotary kiln and setting the rate of rotation and the angle of the reactor so that the residence time of the material in the reactor is sufficient to reduce substantially all of the iron oxide to iron.
  • the method may include preventing ingress of air into the reactor.
  • the feed rates of the iron oxide-containing material and the carbon- containing material and the operating temperature of the reactor may be selected so that a superficial gas flow rate through the reactor caused by the release of gases resulting from the reduction is low enough to prevent any substantial entrainment and consequent loss of the finely divided iron oxide-containing material and carbon- containing material from the reactor.
  • the superficial gas flow rate is less than 2ms "1 , preferably about 1 ms "1 .
  • the method may include controlling iron oxide-containing material and carbon-containing material feed rate, reactor temperature and gas withdrawal rate from the reactor to achieve a substantially steady state concentration of carbon monoxide in the reactor.
  • the method may include the step of recovering excess carbon monoxide withdrawn from the reactor and using the excess carbon monoxide to produce energy.
  • the energy produced may be used to heat the reactor.
  • the product produced according to the method of the invention is a granular iron with a particle size similar to that of the particle size of the iron oxide-containing material.
  • the method may include contacting the iron oxide-containing material with a slight excess of the carbon-containing material (e.g. about 5%-30% excess), magnetically separating product iron from excess carbon-containing material (e.g. distilled duff coal), and melting the iron product, producing mild steel with a purity in excess of 99% by mass.
  • a slight excess of the carbon-containing material e.g. about 5%-30% excess
  • magnetically separating product iron from excess carbon-containing material e.g. distilled duff coal
  • the purity of the iron produced after magnetic removal of carbon is thus typically in excess of 99%. This is the purity of mild steel.
  • the product produced can be in the form of a stainless steel.
  • a method for the production of iron from an iron oxide-containing material including reducing an iron oxide-containing material with a particle size distribution range with a ⁇ 90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a ⁇ 90 of less than 6mm, in a commercial scale reactor at an elevated temperature, the reduction producing carbon monoxide and the method further including feeding the materials into the reactor at a rate and at a temperature, and withdrawing carbon monoxide from the reactor at a rate, selected so that a substantially steady state of concentration of carbon monoxide is maintained in the reactor.
  • the iron oxide-containing material and the carbon-containing material may be as hereinbefore described.
  • the iron oxide-containing material and the carbon-containing material may be fed into the reactor at a rate which is selected so that the carbon monoxide which is produced in the reduction process flows through the reactor at a superficial gas flow rate of less than about 2 ms "1 and preferably at about 1 ms "1 .
  • a method for the production of iron from an iron oxide-containing material including reducing an iron oxide-containing material with a particle size distribution range with a ⁇ 90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a ⁇ 90 of less than 6mm, in a commercial scale reactor, the method further including feeding the materials into the reactor at a rate, and operating the reactor at an elevated temperature, such that a superficial gas flow rate in the reactor caused by the release of gases resulting from the reduction is less than 2ms "1 .
  • the iron oxide-containing material and the carbon-containing material may be as hereinbefore described.
  • the temperature will be between about 1000 ° C and 1 100 ° C and more preferably about 1050 ° C.
  • the superficial gas flow rate will be about 1 ms "1 .
  • substantially all of the iron oxide-containing material is reduced.
  • a reactor assembly suitable for use in the commercial production of iron from an iron oxide- containing material which has a particle size distribution range with a ⁇ 90 of less than about 2mm by contacting the material with a carbon-containing material which has a particle size distribution range with a ⁇ 90 of less than about 6mm at an elevated temperature, the reactor assembly including a generally cylindrical reactor with an inlet and an outlet mounted for rotation about a longitudinal axis thereof, heating means for heating the reactor to a temperature of between about 900 ° C and 1200 ° C and mounting means for mounting the assembly on a vehicle.
  • the heating means may be electrical heating means located external to the reactor.
  • the assembly may include drive means for rotating the reactor.
  • the method extends to a vehicle with a mounted reactor assembly as claimed hereinbefore described.
  • Figure 1 shows a schematic side view of a reactor for use in the method of the invention.
  • Figure 2 shows, schematically, a section through the reactor of Figure 1.
  • reference numeral 10 generally indicates a reactor assembly in the form of an electrically heated rotary kiln for use in the method of the invention.
  • the kiln 10 includes a cylindrical reactor tube 12 housed in an outer casing 14.
  • the casing 14 has a square profile as can be seen in Figure 2 with outer dimensions of about 2 x 2m.
  • the reactor 12 is mounted for rotation on a support frame, generally indicated by reference numeral 16.
  • a feeder 18 feeds raw material into the inlet end 20 of the reactor tube 12.
  • the feeder 18 is provided with a labyrinth seal (not shown) to prevent air flow into the reactor tube 12.
  • the reactor tube 12 is about 6m long with a diameter of about 1 m and is electrically heated by heating elements (not shown) in the casing 14.
  • the kiln 10 slopes from left to right as can be seen in the drawings and the support frame 16 is provided with an adjustment mechanism (not shown) to increase or decrease the slope or angle of the reactor tube 12 which together with varying the speed of rotation changes the rate of passage of raw material through the reactor tube 12.
  • the outlet end 22 of the reactor tube 12 is provided with a seal (not shown) to prevent air contact with the granular iron product as it flows from the reactor tube 12.
  • the frame 16 has support legs 24 which can be mounted on a vehicle (not shown) so that the entire reactor assembly can be transported to an area in which waste iron oxide and/or waste coal has been stockpiled.
  • the reduction mixture (based on 1 ton magnetite) is thus:
  • a good reduced iron powder (from magnetite or haematite), using the method of the invention, typically has the following XRD pattern:
  • the reduced iron powder was fed at 1 kg / minute on to a rotating magnetic drum at 50 rpm with a magnetic strength of 1 200 gauss while the collection gap between magnetic and non magnetic material was set at 10mm.
  • the split between magnetic and non magnetic material is typically 82 - 86% magnetic material and 14 -18 % non magnetic material.
  • the magnetic fraction of the reduced iron powder can be melted using various furnaces e.g. arc, induction or resistance.
  • the magnetic fraction contains between 78 - 82% metal while the gas loss is between 3 - 6%.
  • lime is normally blended with the magnetic iron powder before it is fed into the furnace. This helps with fluxing of the slag and to remove P and S from the iron.
  • Arc and induction furnaces usually operate under oxidative conditions which assist with the removal of P from iron into the slag. Normally the oxidative conditions (high FeO content) in the slag prevent the removal of S from the iron and this is then done in a ladle. A typical ladle slag to remove S from iron is used in this ratio to the molten iron:
  • This clean mild steel master batch (re-bar or flat iron), of which the S and P ⁇ 0.06% and C ⁇ 0.25%, can be used to produce various types of stainless steel by the addition of various alloys to it such as FeCr, FeMn, FeSi, FeV, FeMo, FeC 3 etc. Even more, these different types of alloys can be blended with the magnetic iron powder (and lime) before melting to obtain the correct product after desulphurization and dephosphohzation.
  • Total energy needed 5 216.4 MJ to yield 643kg iron, or 2.25 MWh per ton of iron.
  • the reduction mixture (based on 1 ton haematite) is thus:
  • the minimum tube diameter for a superficial gas velocity ⁇ 1 m/s can be calculated as follows (assuming voidage approximates 1 ):
  • the superficial gas velocity per second will be 0.482m 3 /s.
  • the method of the invention is compared with the traditional blast furnace method of manufacturing iron the main differences are the following. Firstly, the blast furnace is replaced by a rotary kiln. The refractory lining of the blast furnace is not required and the method of the invention is conducted in a stainless steel tubular reactor.
  • the feed material used in the blast furnace generally has a particle size greater than 6 mm whilst the feed used in the method of the invention is a waste material which has a particle size of less then 0.5 mm.
  • Heating a blast furnace is internal via fossil fuel and carbon monoxide whilst heating of the rotary kiln is by external electric heating.
  • the method of the invention operates at low superficial gas velocities, typically less than 2ms "1 to avoid entrainment of the finally powdered reactants.
  • a blast furnace operates at a temperature gradient of between about 200 0 C and 1600 0 C, in the method of the invention, as illustrated, the entire process is carried out at a constant temperature of 1050 0 C.
  • the product from the traditional blast furnace is liquid iron whereas the product of the method of the invention is a fine granular iron powder.
  • the by-product from a blast furnace is carbon dioxide and operating a blast furnace requires a carbonaceous flux whereas the by- product of the method of the invention is carbon monoxide, which can be used to generate electricity, and the method of the invention requires metal oxide fluxes.
  • the reactor of the invention can be transported to an area in which it is required. In this way costs are substantially reduced because the raw materials do not have to be transported to the reactor.
  • the granular iron product is produced with little or no associated dust. It is also an advantage of the invention illustrated that the high surface area of the finely divided iron oxide and coal increases the rate of reduction and reduces the retention time in the rotary kiln. This, in turn, means an increased throughput when compared with a blast furnace.
  • the Applicant estimates that the cost per ton of iron produced by the method of the invention will be about one half of the cost per ton of pig iron produced in a conventional blast furnace.
  • the XRD powder pattern of the reduced material in Example 1 indicates a high reduction efficiency (ratio between Fe and FeO). This arises because of the control over the reduction process which is possible by the method of the invention.
  • the product is an iron powder and not a molten mass. This permits the addition of additives to the iron powder prior to melting it. In this regard, it is far more difficult to add additives and mix such additives homogeneously into a molten mass. This in turn means that the carbon level after reduction can be controlled more efficiently by mixing an oxidizing agent such as Fe 2 Os with the iron powder prior to melting. It is also possible to add other metals or metal oxides to the iron powder prior to melting.
  • the method of the invention does not use the carbon monoxide formed in the reduction process to generate energy internally by reacting it with oxygen.
  • the method of the invention produces relatively pure carbon monoxide gas as a by-product and this can be used externally as a fuel source to generate electricity via a steam generator.
  • the invention in particular, allows the thousands of tons of waste iron oxide and waste coal which is available in many parts of the world to be profitably converted to iron.

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  • Metallurgy (AREA)
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Abstract

A method for the production of iron from an iron oxide-containing material includes contacting an iron oxide-containing material with a particle size distribution range with a ∂90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a ∂90 of less than 6mm, in a commercial scale reactor at a temperature of between 900°C and 1200°C for a contact time sufficient to reduce the iron oxide to iron.

Description

A METHOD FOR THE COMMERCIAL PRODUCTION OF IRON
THIS INVENTION relates to a method for the commercial production of iron. It also relates to a reactor assembly and a vehicle for use in the commercial production of iron.
In historical times, iron was produced by reducing iron oxide with charcoal.
In this process, the charcoal acted both as the source of heat and as the reducing agent. The product was an alloy consisting of about 96,5% iron and about 3,5% carbon. Charcoal was later supplanted by coke. At present, iron is produced largely from the iron ores haematite (Fe2Os) and magnetite (Fβ3θ4) by carbothermic reduction in a blast furnace at temperatures of about 20000C. In this process, the iron ore, carbon in the form of coke and a flux such as limestone are fed into the top of the furnace and a blast of heated air is forced into the bottom of the furnace. In the furnace, the coke reacts with oxygen in the air blast to produce carbon monoxide and the carbon monoxide reduces the iron ore to iron, becoming oxidised to carbon dioxide in the process. The iron produced in this process is called pig iron. As a result of the high gas flow rate in blast furnaces, the iron oxide and coke have to be in relatively coarse particulate form, preferably with particle sizes larger than about 6mm. If the particle size is substantially less than 6mm, the feedstock will simply be blown out of the top of the blast furnace by the gas stream. In addition, there are inherent problems associated with the operation of blast furnaces in preventing the formation of hot and cold zones which can result in back reactions and competing reactions.
In the mining, transport and storage of iron ore and coal, large amounts of iron oxide fines and coal fines, usually referred to as duff, are produced. Finely divided iron oxide is also produced as a by-product both in the production of copper, e.g. in the case of Phalaborwa Mining Corporation in South Africa or Freeport (Grasberg) in Indonesia and from the roasting of FeS2 in the production of sulphuric acid. These finely divided materials could provide a source of raw material for the production of iron. However, for the reasons set out above, unless these materials are first granulated, they cannot be used in blast furnaces, but granulation is not economically viable. It is an object of the invention to address this problem.
According to one aspect of the invention, there is provided a method for the production of iron from an iron oxide-containing material, the method including contacting an iron oxide-containing material with a particle size distribution range with a θ90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a θ90 of less than 6mm, in a commercial scale reactor at a temperature of between 900°C and 1200°C for a contact time sufficient to reduce the iron oxide to iron.
Preferably, substantially all of the iron oxide-containing material is reduced to iron.
As is well known to those skilled in the art, θ90 means that at least 90% of the material has a particle size less than that specified, i.e. a θ90 of 2mm means that at least 90% of the particulate material has a particle size of less than 2mm. θ90 is also often simply written as d90.
By "commercial scale reactor" is meant a reactor capable of routinely producing at least 1000 kg/h of iron.
The iron oxide-containing material may have a θ90 of less than 1 mm. PPrreeffeerraabbllyy,, ttrhe iron oxide-containing material has a θ90 of less than 500μm.
TThhee ccaarrbboonn--ccoonnttaaiinniinngg mmaatteerriiaall n may have a θ90 of less than 2mm. Preferably, the carbon-containing material has a θ90 of less than 1 mm.
The contact time may be between 30 minutes and 360 minutes. The contact time is preferably between about 60 minutes and about 180 minutes and more preferably about 120 minutes. The method may include contacting the iron oxide-containing material with the carbon-containing material in the presence of a flux such as calcium oxide or quicklime.
The iron oxide-containing material may be waste iron oxide. It may in particular be the waste product produced in the mining of iron ore, in the production of copper or in the production of sulphuric acid. This material typically has a particle size with a θ90 of less than about 500μm and usually consists of haematite or magnetite. The carbon-containing material may be waste coal or coal fines, often referred to as duff which is produced during the mining and transport of coal. Instead, the carbon- containing material may be the waste material produced in the distillation or devolatilisation of coal.
The carbon-containing material is preferably de-volatilised coal fines. This material typically has a particle size with a θ90 of less than about 6mm.
The temperature in the reactor may be between 10000C and 1 1000C, e.g. about 1050°C.
The method may include heating the reactor using an external heat source. Typically, the reactor is heated electrically.
By carrying out the reduction at a temperature of about 10500C using external electric heating, the method of the invention can be carefully controlled. The equilibrium between CO and CO2 at different temperatures is set out below:
CO CO2
450°C: 2% 98%
750°C 76% 24%
10500C 99.6% 0.4%
Thus by controlling the temperature at approximately 10500C the CO/CO2 equilibrium lays almost entirely on the CO side. The traditional method of making iron as carried out in blast furnaces requires the use of carbonaceous fluxes, such as CaCO3 to increase the CO2 concentration inside the furnace. However, this not only increases the gas velocity but the decomposition of CaCO3 is endothermic and increases the energy demand. The decomposition of CaCO3 occurs at about 9000C,
CaCO3 = CaO + CO2
temp: 5000C 600°C 7000C 800°C 900°C mm Hg: 0.1 1 2.35 25.3 168 760
The formation of FeSiO3 and Fe2SiO4 occurs from above 7000C and active CaO is needed to react with the SiO2 before it combines with the FeO.
Contacting the iron oxide-containing material with the carbon-containing material may include feeding pre-determined quantities of said materials into a rotating cylindrical reactor or rotary kiln and setting the rate of rotation and the angle of the reactor so that the residence time of the material in the reactor is sufficient to reduce substantially all of the iron oxide to iron.
The method may include preventing ingress of air into the reactor.
The feed rates of the iron oxide-containing material and the carbon- containing material and the operating temperature of the reactor may be selected so that a superficial gas flow rate through the reactor caused by the release of gases resulting from the reduction is low enough to prevent any substantial entrainment and consequent loss of the finely divided iron oxide-containing material and carbon- containing material from the reactor. Typically, the superficial gas flow rate is less than 2ms"1 , preferably about 1 ms"1.
The method may include controlling iron oxide-containing material and carbon-containing material feed rate, reactor temperature and gas withdrawal rate from the reactor to achieve a substantially steady state concentration of carbon monoxide in the reactor.
The method may include the step of recovering excess carbon monoxide withdrawn from the reactor and using the excess carbon monoxide to produce energy. The energy produced may be used to heat the reactor.
The product produced according to the method of the invention, at least initially, is a granular iron with a particle size similar to that of the particle size of the iron oxide-containing material.
The method may include contacting the iron oxide-containing material with a slight excess of the carbon-containing material (e.g. about 5%-30% excess), magnetically separating product iron from excess carbon-containing material (e.g. distilled duff coal), and melting the iron product, producing mild steel with a purity in excess of 99% by mass.
The purity of the iron produced after magnetic removal of carbon is thus typically in excess of 99%. This is the purity of mild steel. In addition, by adding suitable quantities of chromium, nickel or manganese, the product produced can be in the form of a stainless steel.
According to another aspect of the invention, there is provided a method for the production of iron from an iron oxide-containing material, the method including reducing an iron oxide-containing material with a particle size distribution range with a θ90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a θ90 of less than 6mm, in a commercial scale reactor at an elevated temperature, the reduction producing carbon monoxide and the method further including feeding the materials into the reactor at a rate and at a temperature, and withdrawing carbon monoxide from the reactor at a rate, selected so that a substantially steady state of concentration of carbon monoxide is maintained in the reactor. The iron oxide-containing material and the carbon-containing material may be as hereinbefore described.
The iron oxide-containing material and the carbon-containing material may be fed into the reactor at a rate which is selected so that the carbon monoxide which is produced in the reduction process flows through the reactor at a superficial gas flow rate of less than about 2 ms"1 and preferably at about 1 ms"1.
According to yet another aspect of the invention, there is provided a method for the production of iron from an iron oxide-containing material, the method including reducing an iron oxide-containing material with a particle size distribution range with a θ90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a θ90 of less than 6mm, in a commercial scale reactor, the method further including feeding the materials into the reactor at a rate, and operating the reactor at an elevated temperature, such that a superficial gas flow rate in the reactor caused by the release of gases resulting from the reduction is less than 2ms"1.
The iron oxide-containing material and the carbon-containing material may be as hereinbefore described.
Preferably, the temperature will be between about 1000°C and 1 100°C and more preferably about 1050°C.
Preferably the superficial gas flow rate will be about 1 ms"1.
Preferably, substantially all of the iron oxide-containing material is reduced.
According to a further aspect of the invention, there is provided a reactor assembly suitable for use in the commercial production of iron from an iron oxide- containing material which has a particle size distribution range with a θ90 of less than about 2mm by contacting the material with a carbon-containing material which has a particle size distribution range with a θ90 of less than about 6mm at an elevated temperature, the reactor assembly including a generally cylindrical reactor with an inlet and an outlet mounted for rotation about a longitudinal axis thereof, heating means for heating the reactor to a temperature of between about 900°C and 1200°C and mounting means for mounting the assembly on a vehicle.
The heating means may be electrical heating means located external to the reactor. The assembly may include drive means for rotating the reactor.
The method extends to a vehicle with a mounted reactor assembly as claimed hereinbefore described.
The invention is now described, by way of example, with reference to the following Examples and drawings in which
Figure 1 shows a schematic side view of a reactor for use in the method of the invention; and
Figure 2 shows, schematically, a section through the reactor of Figure 1.
Referring to the drawings, reference numeral 10 generally indicates a reactor assembly in the form of an electrically heated rotary kiln for use in the method of the invention. The kiln 10 includes a cylindrical reactor tube 12 housed in an outer casing 14. The casing 14 has a square profile as can be seen in Figure 2 with outer dimensions of about 2 x 2m. The reactor 12 is mounted for rotation on a support frame, generally indicated by reference numeral 16. A feeder 18 feeds raw material into the inlet end 20 of the reactor tube 12. The feeder 18 is provided with a labyrinth seal (not shown) to prevent air flow into the reactor tube 12.
The reactor tube 12 is about 6m long with a diameter of about 1 m and is electrically heated by heating elements (not shown) in the casing 14. The kiln 10 slopes from left to right as can be seen in the drawings and the support frame 16 is provided with an adjustment mechanism (not shown) to increase or decrease the slope or angle of the reactor tube 12 which together with varying the speed of rotation changes the rate of passage of raw material through the reactor tube 12. The outlet end 22 of the reactor tube 12 is provided with a seal (not shown) to prevent air contact with the granular iron product as it flows from the reactor tube 12. The frame 16 has support legs 24 which can be mounted on a vehicle (not shown) so that the entire reactor assembly can be transported to an area in which waste iron oxide and/or waste coal has been stockpiled.
Example 1
Magnetite from Phalaborwa Mining Company, South Africa with the following composition and size distribution was used in this Example:
Fe 66%
Fe3O4 91.2%
SiO2 0.52%
AI2O3 1.08%
Sulphur 0.1 1 %
Phosphor 0.04% a90 -250μm a50 -106μm a10 -15μm
700 kg coal (refer to table 1 ) was devolatized to produce 400 kg devolatized coal as shown below:
900°C
700kg 400kg (Under reducing conditions)
Tablei
Figure imgf000009_0001
Figure imgf000010_0001
The following formula represents the reduction equation for the magnetite:
Fe3O4 + 4C = 3Fe + 4CO(g)
Based on 1 mol Fe3O4, the following calculations can be done:
1 mol Fe3O4 = 231.54g, 91.2% purity = 253.88g 4mol C = 48g, 73% purity = 65.75g + 50% excess devolatized coal = 98.625g (to exclude air in rotary)
It follows that, to reduce 1 ton magnetite in the rotary, you need 388kg devolatized coal. 1 ton magnetite contains 10.8kg AI2O3 and 5.2kg SiO2. 388kg devolatized coal contains 38.8kg SiO2 and 15.5kg AI2O3. Total SiO2 = 44kg = 0.733kmol and total AI2O3 = 26.3kg = 0.258kmol. It was found that if equal mol amounts of lime are added to the mol amounts of SiO2 and AI2O3, sintering during reduction is greatly minimized. Total lime needed = 0.991 kmol CaO = 55.5kg, 89% purity = 62.4kg. The lime is milled to -500μm, 350 =125μm.
The reduction mixture (based on 1 ton magnetite) is thus:
1 ton Magnetite (91.2%) (dried at 3000C) 388kg devolatized coal (73%) 62kq lime (89%) 1450kg
2.9 tons of the reduction mixture was fed into a 9.7m long, 0.96m ID inclined reduction tube or rotary kiln at a feed rate of 300kg/h. The tube was rotated at 1.12 rpm and material from the tube was collected in drums. After approximately 2h, the first material was collected (refer to Table 2 below). The tube had 3 firing zones, namely zone 1 which is a feed zone, zone 2 which is a middle zone and zone 3 which is a discharge zone. The temperature in each zone was measured and is indicated in Table 2. To prevent the material from sticking to the sides, 2 mechanical hammers were used, at the feed end and the discharge end of the tube. The angle of the tube was equivalent to a drop of 5mm / 1 m over the length of the tube. Steady state r period, mass feed = 2000kg
Figure imgf000011_0001
After 10 hours the oven was switched off, and a CO2 (g) flame combusting CO withdrawn from the tube still burned for another hour. Overnight, another 147kg was discharged from the rotary while a bed load of 179kg remained in the rotary. This material was discarded as it re-oxidized due to a lack of a CO-atmosphere. The material in drums 1 and 16 was also discarded.
According to the reduction equation given above, complete reduction of
253.9g magnetite feed will result in 1 12g CO (g) loss. Therefore, from a reduction mixture of 1450kg, 441 kg CO (g) should evolve. This equals a mass loss of 30.4%. Depending on the efficiency of a rotary seal used to exclude air from the reduction tube and thus from the reduction process, the mass loss during steady state phase of reduction is normally between 34 - 37%. Care must also be taken to prevent the hot iron powder from re-oxidizing. This is normally achieved by water cooling of a chamber where the iron powder is fed through.
A good reduced iron powder (from magnetite or haematite), using the method of the invention, typically has the following XRD pattern:
CaO 2 - 5% Haematite (Fe2O3) 1 - 2%
Iron 85 - 89%
Magnetite (Fe3O4) O - 1 %
Carbon 2 - 6% Wuestite (FeO) 1 - 4%
It was discovered that a high purity Fe (mild steel) could be obtained if the reduced powder was magnetically separated from the excess coal and other non magnetic impurities before melting. The table below shows the difference in quality of reduced powder that was melted as is v/s the melt of the magnetic fraction of reduced iron.
Melted reduced powder Melted magnetic fraction
Fe 96 - 97% > 99%
C 2 - 3% < 0.25%
Si 1 - 2% < 0.25%
S 0.2 - 0.5% approx 15% reduction in S
P 0.05 - 0.2% approx 30% reduction in P
The reduced iron powder was fed at 1 kg / minute on to a rotating magnetic drum at 50 rpm with a magnetic strength of 1 200 gauss while the collection gap between magnetic and non magnetic material was set at 10mm. The split between magnetic and non magnetic material is typically 82 - 86% magnetic material and 14 -18 % non magnetic material.
The magnetic fraction of the reduced iron powder can be melted using various furnaces e.g. arc, induction or resistance.
Normally, the magnetic fraction contains between 78 - 82% metal while the gas loss is between 3 - 6%. Between 5 - 10% lime is normally blended with the magnetic iron powder before it is fed into the furnace. This helps with fluxing of the slag and to remove P and S from the iron. Arc and induction furnaces usually operate under oxidative conditions which assist with the removal of P from iron into the slag. Normally the oxidative conditions (high FeO content) in the slag prevent the removal of S from the iron and this is then done in a ladle. A typical ladle slag to remove S from iron is used in this ratio to the molten iron:
2% CaC2 (milled) 1.5% CaF2 powder
3% AI2O3 powder
8.5% lime (milled)
0.4% Al buttons
Unlike arc or induction furnaces, the atmosphere in carbon resistant furnaces is reducing. Depending on the P content in the iron, with the lime addition, sometimes it is necessary to blend 2 - 5% Fe2O3 powder to the magnetic iron powder in order to oxidize the P for it to be absorbed into the basic slag. In this case it is possible to extract both the S and P from the iron at the same time using the same slag.
By using this process (reduction of fines into iron powder in accordance with the method of the invention, magnetic separation of iron powder, homogenous addition of additives to the magnetic iron powder before melting and controlled melting of the powder) the production, directly from iron ore fines, of a mild steel master batch without going through the intermediate of pig iron, is possible.
This clean mild steel master batch (re-bar or flat iron), of which the S and P < 0.06% and C < 0.25%, can be used to produce various types of stainless steel by the addition of various alloys to it such as FeCr, FeMn, FeSi, FeV, FeMo, FeC3 etc. Even more, these different types of alloys can be blended with the magnetic iron powder (and lime) before melting to obtain the correct product after desulphurization and dephosphohzation.
The following calculations illustrate energy considerations for the process of the invention:
Energy required for heating the reduction mixture:
1 ton magnetite from 200C to 1 0500C, ΔT = 1 030°C
CpMΔT = 1 x 1 t x 1 0300C = 1 030 MJ
388kg devol. coal from 20°C to 1 050°C, ΔT = 1 0300C
CpMΔT = 1.7 x 0.388t x 1 030°C = 679.4 MJ
62kg lime from 20°C to 1 0500C, ΔT = 1 030°C
CpMΔT = 0.8 x 0.062t x 1 030°C = 51 .O MJ
1 760.4 MJ Energy required to reduce iron at 1 0500C:
Fe3O4 + 4C = 3Fe + 4CO (g) 2 734 MJ
However, the magnetite used in this Example was only 91.2% pure = 2
493.4 MJ is needed. Typically the mass retained after reduction is 66% (1 450kg) = 957kg reduced powder.
Normally, approximately 84% of the reduced powder is recovered as the magnetic fraction = 804kg.
The energy required to melt this powder at 1 535°C: 804kg + 80kg additive = 884kg is heated from 200C to 1 535°C, ΔT = 1 515°C
CpMΔT = 0.6 x 0.884t x 1 515°C = 803.6 MJ
At least 80% of the magnetic fraction (804kg) = 643kg is recovered as iron. Energy needed to turn Fe (s) into Fe [I) = 247 KJ/kg Fe, thus 159 MJ is needed for 643kg iron.
Total energy needed = 5 216.4 MJ to yield 643kg iron, or 2.25 MWh per ton of iron.
A ton of magnetite from Phalaborwa Mining Company contains 660kg of iron. This means a recovery of 643kg = 97.4% efficiency.
As mentioned before, a ton of Phalaborwa Mining Company magnetite releases 441 kg CO (g) during reduction. When a kg of CO(g) burns in air, 10.2 MJ of energy is released. This means that 4 498.2 MJ of energy is released when 441 kg CO(g) burns in air.
During the devolatization of coal, approximately 700kg of coal is used to produce 400kg devolatized coal. Release of energy to obtain 400kg of devolatized coal:
(700kg x 28) - (400kg x 25) = 19 600 - 10 000
= 9 600 MJ During the reduction of 1 ton Phalaborwa Mining Company magnetite, 388kg devolatized coal is used, meaning 388 / 400 x 9 600 = 9 312 MJ of energy is released during devolatization.
The total energy release to reduce 1 ton of Phalaborwa Mining Company magnetite = 13 810 MJ. If 30% of this energy could be turned into electrical energy via steam generation, 4 143 MJ per 643kg Fe produced or 1.79 MWh/ton iron could be recovered. This means that approximately 75% of the energy required to produce 1 ton of iron could be obtained from the process.
Example 2
Haematite from Sishen, South Africa with the following composition and size distribution was used in this Example:
Fe 63.1 %
Fe2O3 90.2%
SiO2 5.6%
AI2O3 1.98%
S 0.03%
P 0.14% a90 -800μm a50 -500μm a10 -200μm
The following formula represents the reduction equation for the haematite:
Fe2O3 + 3C = 2Fe + 3CO(g)
Based on 1 mol Fe2O3, the following calculations can be done:
1 mol Fe2O3 = 159.7g, 90.2% purity = 177g 3mol C = 36g, 73% purity = 49.32g + 50% excess devolatized coal = 73.97g (to exclude air in rotary) It follows that, to reduce 1 ton haematite in the rotary kiln, you need 418kg devolatized coal. 1 ton haematite contains 19.8kg AI2O3 and 56 kg SiO2. 418kg devolatized coal contains 41.8kg SiO2 and 16.7kg AI2O3. Total SiO2 = 97.8kg = 1.63 kmol and total AI2O3 = 36.5kg = 0.358 kmol. Total CaO needed = 1.988 kmol = 1 1 1.33kg, 89% purity = 125kg.
The reduction mixture (based on 1 ton haematite) is thus:
1 ton haematite (90.2%) (dried at 3000C) 418kg devolatized coal (73%)
125kq lime (89%) 1543kg
This material was reduced just like the magnetite in Example 1 and similar results were obtained.
The minimum tube diameter for a superficial gas velocity <1 m/s can be calculated as follows (assuming voidage approximates 1 ):
450kg CO = 16 kmol of gas
At STP, 1 mol gas = 22.4« (273k)
Therefore, 16 kmol gas = 16 000 x 22.4«
= 358.4 m3
At 10500C (1323k) = 1323 x 358.4m3
273 = 1736.86m3
If the reduction reaction occurs over an hour, the superficial gas velocity per second will be 0.482m3/s.
Area of cylinder = — χ δ2
Volume / s = area x velocity Therefore, 0.482m3/s = -χ δ2
4
If v = 1 m/s the tube diameter is
4 x 0.482
= 0.783m πx l
If a tube with a diameter of 1 m and a length of 6m is used, the volume of the tube would be 4700«. A 15% bed load would be 705«. The bulk density of the feed mixture is approximately 2g / mE, therefore 705« load will have a mass of 1410kg. This means if 1450kg of blended material (example 1 ) is fed per hour at 10500C (product temperature) through a rotary kiln with the above dimensions, the superficial gas velocity would be less than 1 ms"1.
If the method of the invention, as illustrated, is compared with the traditional blast furnace method of manufacturing iron the main differences are the following. Firstly, the blast furnace is replaced by a rotary kiln. The refractory lining of the blast furnace is not required and the method of the invention is conducted in a stainless steel tubular reactor. The feed material used in the blast furnace generally has a particle size greater than 6 mm whilst the feed used in the method of the invention is a waste material which has a particle size of less then 0.5 mm. Heating a blast furnace is internal via fossil fuel and carbon monoxide whilst heating of the rotary kiln is by external electric heating. In addition, where a blast furnace operates at gas velocities in excess of 10 ms"1 the method of the invention operates at low superficial gas velocities, typically less than 2ms"1 to avoid entrainment of the finally powdered reactants. Further, where a blast furnace operates at a temperature gradient of between about 2000C and 16000C, in the method of the invention, as illustrated, the entire process is carried out at a constant temperature of 10500C. The product from the traditional blast furnace is liquid iron whereas the product of the method of the invention is a fine granular iron powder. Further, the by-product from a blast furnace is carbon dioxide and operating a blast furnace requires a carbonaceous flux whereas the by- product of the method of the invention is carbon monoxide, which can be used to generate electricity, and the method of the invention requires metal oxide fluxes. Of particular economic importance, where a blast furnace has a fixed locality, the reactor of the invention can be transported to an area in which it is required. In this way costs are substantially reduced because the raw materials do not have to be transported to the reactor.
It is also an advantage of the invention illustrated that the granular iron product is produced with little or no associated dust. It is also an advantage of the invention illustrated that the high surface area of the finely divided iron oxide and coal increases the rate of reduction and reduces the retention time in the rotary kiln. This, in turn, means an increased throughput when compared with a blast furnace. The Applicant estimates that the cost per ton of iron produced by the method of the invention will be about one half of the cost per ton of pig iron produced in a conventional blast furnace.
The XRD powder pattern of the reduced material in Example 1 indicates a high reduction efficiency (ratio between Fe and FeO). This arises because of the control over the reduction process which is possible by the method of the invention. It is a further advantage of the invention illustrated that the product is an iron powder and not a molten mass. This permits the addition of additives to the iron powder prior to melting it. In this regard, it is far more difficult to add additives and mix such additives homogeneously into a molten mass. This in turn means that the carbon level after reduction can be controlled more efficiently by mixing an oxidizing agent such as Fe2Os with the iron powder prior to melting. It is also possible to add other metals or metal oxides to the iron powder prior to melting. It is a particular advantage of the invention that, by magnetically removing excess coal from the iron product prior to smelting, the quality of the iron is substantially improved to the extent that it meets the specifications of mild steel. This results in a substantial increase in the value of the product. As mentioned above, it is also possible to produce a stainless steel ingot instead of a pig- iron ingot. In this way, the value of the product can be further substantially increased in that a stainless steel may be produced directly from an iron oxide reduction process without the intermediacy of further smelting processes. This represents a very substantial improvement on existing methods for producing stainless steel. It is a further advantage of the invention that, unlike, traditional methods, the method of the invention does not use the carbon monoxide formed in the reduction process to generate energy internally by reacting it with oxygen. The method of the invention produces relatively pure carbon monoxide gas as a by-product and this can be used externally as a fuel source to generate electricity via a steam generator. The invention, in particular, allows the thousands of tons of waste iron oxide and waste coal which is available in many parts of the world to be profitably converted to iron.

Claims

CLAIMS:
1. A method for the production of iron from an iron oxide-containing material, the method including contacting an iron oxide-containing material with a particle size distribution range with a θ90 of less than 2mm, with a carbon-containing material with a particle size distribution range with a θ90 of less than 6mm, in a commercial scale reactor at a temperature of between 900°C and 1200°C for a contact time sufficient to reduce the iron oxide to iron.
2. The method as claimed in claim 1 , in which the iron oxide-containing material has a θ90 of less than 1 mm.
3. The method as claimed in claim 2, in which the iron oxide-containing material has a θ90 of less than 500μm.
4. The method as claimed in any of the preceding claims, in which the carbon-containing material has a θ90 of less than 2mm.
5. The method as claimed in claim 4, in which the carbon-containing material has a θ90 of less than 1 mm.
6. The method as claimed in any of the preceding claims, in which the contact time is between 30 minutes and 360 minutes.
7. The method as claimed in any of the preceding claims, in which the carbon-containing material is de-volatilised coal fines.
8. The method as claimed in any of the preceding claims, in which the temperature in the reactor is between 10000C and 1 1000C.
9. The method as claimed in any of the preceding claims, which includes heating the reactor using an external heat source.
10. The method as claimed in claim 9, in which the reactor is heated electrically.
1 1 . The method as claimed in any of the preceding claims, in which contacting the iron oxide-containing material with the carbon-containing material includes feeding pre-determined quantities of said materials into a rotating cylindrical reactor or rotary kiln and setting the rate of rotation and the angle of the reactor so that the residence time of the material in the reactor is sufficient to reduce substantially all of the iron oxide to iron.
12. The method as claimed in any of the preceding claims, which includes preventing ingress of air into the reactor.
13. The method as claimed in any of the preceding claims, in which the feed rates of the iron oxide-containing material and the carbon-containing material and the operating temperature of the reactor are selected so that a superficial gas flow rate through the reactor caused by the release of gases resulting from the reduction is less than 2ms"1.
14. The method as claimed in any of the preceding claims, which includes controlling iron oxide-containing material and carbon-containing material feed rate, reactor temperature and gas withdrawal rate from the reactor to achieve a substantially steady state concentration of carbon monoxide in the reactor.
15. The method as claimed in any of the preceding claims, which includes contacting the iron oxide-containing material with a slight excess of the carbon- containing material, magnetically separating product iron from excess carbon-containing material, and melting the iron product, producing mild steel with a purity in excess of 99% by mass.
16. A reactor assembly suitable for use in the commercial production of iron from an iron oxide-containing material which has a particle size distribution range with a θ90 of less than about 2mm by contacting the material with a carbon-containing material which has a particle size distribution range with a θ90 of less than about 6mm at an elevated temperature, the reactor assembly including a generally cylindrical reactor with an inlet and an outlet mounted for rotation about a longitudinal axis thereof, heating means for heating the reactor to a temperature of between about 900°C and 1200°C and mounting means for mounting the assembly on a vehicle.
17. The reactor assembly as claimed in claim 16, in which the heating means is electrical heating means located external to the reactor.
18. A vehicle with a mounted reactor assembly as claimed in claim 16 or claim 17.
PCT/IB2007/053016 2006-08-01 2007-07-31 A method for the commercial production of iron WO2008020357A2 (en)

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DE602007014062T DE602007014062D1 (en) 2006-08-01 2007-07-31 METHOD FOR THE INDUSTRIAL MANUFACTURE OF IRON
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AT07825975T ATE506457T1 (en) 2006-08-01 2007-07-31 METHOD FOR THE INDUSTRIAL PRODUCTION OF IRON
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