KR101798731B1 - Method for manufacturing iron oxide - Google Patents

Method for manufacturing iron oxide Download PDF

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KR101798731B1
KR101798731B1 KR1020150185815A KR20150185815A KR101798731B1 KR 101798731 B1 KR101798731 B1 KR 101798731B1 KR 1020150185815 A KR1020150185815 A KR 1020150185815A KR 20150185815 A KR20150185815 A KR 20150185815A KR 101798731 B1 KR101798731 B1 KR 101798731B1
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iron
nickel
roasting
chloride
iron oxide
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KR20170076853A (en
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박진균
변태봉
이재영
우광선
이택근
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주식회사 포스코
재단법인 포항산업과학연구원
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/06Ferric oxide [Fe2O3]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention relates to a method for producing iron oxide by roasting a ferric chloride crystal.

Description

[0001] METHOD FOR MANUFACTURING IRON OXIDE [0002]

The present invention relates to a method for producing iron oxide by roasting iron chloride.

The process of iron oxide production by roasting iron chloride crystals, iron chloride, more precisely, involves the following reaction depending on the temperature.

(1) FeCl 4 .4H 2 O (s)? FeCl 2 .2H 2 O (s) + 2H 2 O (1) (> 76 ° C)

(2) FeCl 2 .2H 2 O (s)? FeCl 2 .H 2 O (s) + H 2 O (g)

(3) FeCl 2 · H 2 O (s) → FeCl 2 (s) + H 2 O (g) (> 164 ℃)

(4) 2FeCl 2 (s) + 2H 2 O (g) + 1 / 2O 2 → Fe 2 O 3 (s) + 4HCl (g) (> 250 ℃)

The crystal number (H 2 O) contained in the iron chloride crystals in the roasting process is removed at a low temperature during the roasting process (the process of the above formulas (1) to (3)). Therefore, it does not participate in the oxidation reaction of FeCl 2 (the above formula (4)).

Particularly, iron chloride has high reactivity as a concentrate containing Cl at a high concentration. Therefore, iron chloride has a high reactivity at a high temperature, and it can be produced as FeCl 3 gas phase to FeOCl Chloride is produced.

(5) 3FeCl 2 (s) + 2HCl (g) + 1 / 2O 2 (g) → (FeCl 3) 2 (g) + H 2 O (g)

(6) (FeCl 3 ) 2 (g) + 2Fe 2 O 3 (s)? 6 FeOCl (s)

Due to the generation of such complex chlorides, the recovery rate of iron oxide obtained through roasting is reduced, and chlorides are deposited in the furnace, thereby causing problems such as clogging and defects in the roasting furnace.

One aspect of the present invention is to provide a method for producing iron oxide by roasting iron chloride, which can improve the recovery rate and quality of iron oxide and improve the life of the roasting furnace.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

One aspect of the present invention is a method for preparing a ferric chloride solution, comprising: preparing a ferric chloride crystal; And

Roasting the iron chloride crystals in a roasting furnace to form iron oxide,

And steam is introduced into the roasting furnace during roasting.

INDUSTRIAL APPLICABILITY According to the present invention, recovery of iron oxide is improved in roasting a ferric chloride crystal, and in particular, the concentration of Cl in iron oxide obtained is low, so that iron oxide having excellent quality can be improved.

Further, in the present invention, the deposition amount of the chloride is reduced, and the lifetime of the roasting furnace can be improved, which results in cost reduction and prevention of environmental pollution.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have found that, in the process of producing iron oxide by roasting a ferric chloride crystal, iron chloride contains a high concentration of Cl, and in order to solve the problem of forming a complex chloride according to conditions such as moisture in combustion air at high temperature, As a result, the present invention has been achieved.

The present invention includes a step of preparing iron chloride crystals, and roasting the iron chloride crystals in a roasting furnace to form iron oxide.

It is preferable that the iron chloride crystals contain an Fe component of 30 wt% or more, and impurities such as Mg, Mn, Ca, and Si do not exceed 5 wt% in total. When a large amount of the impurities are present, the Cl decomposition characteristic may be changed by the impurity to increase the Cl concentration in the final product.

In the present invention, steam is introduced during roasting in the roasting furnace to form iron oxide. The introduction of the water vapor is intended to suppress the generation of Cl 2 gas which can increase the reaction rate of removing HCl from the Cl which is bound to the iron chloride crystals by reaction with water vapor (H 2 O) and cause environmental problems. In addition, the partial pressure of the HCl gas generated in the roasting furnace is diluted to suppress the production of FeCl 3 gas, thereby improving the iron oxide recovery rate and reducing the impurity inclusion in the recovered acid in the acid recovery process.

The amount of steam to be added is preferably 40 to 70% by weight of the raw material. If the amount of water vapor is less than 40% by weight of the raw material, there may be a problem that the Cl concentration in the iron oxide produced may be increased due to a decrease in the reactivity of the roasting, and a problem may occur when the Cl gas leaks due to the exhaustion of the roasted iron chloride crystals . On the other hand, if it exceeds 70%, there may arise a problem in the roasting burner burning, and the reactivity of roasting of the iron chloride may be lowered due to the relatively low oxygen partial pressure.

In the roasting furnace, it is preferable to apply heat by using a combustion burner in order to supply sufficient oxygen and roasting reaction. In the combustion burner, proper mixing of fuel and air is important, and the air-fuel ratio (air / fuel weight ratio) at this time is preferably 1.4 to 2.4. If the air-fuel ratio is less than 1.4, the reactivity to roasting is lowered and the Cl concentration in the iron oxide increases and the problem of exhaustion of undrawn iron chloride crystals occurs. When the air-fuel ratio exceeds 2.4, the recovery rate due to the FeCl 3 gas phase is lowered due to the relatively high oxygen partial pressure And there is a problem that impurity inclusion in the acid-recovering step-recovering acid increases.

At the roasting, the temperature of the roasting furnace is preferably 500 to 700 ° C. The roasting reaction of the iron chloride crystals proceeds at 250 DEG C, but the roasting temperature is preferably maintained at 500 DEG C or higher in order to ensure an appropriate reaction rate. If the melting temperature of the iron chloride crystals is 653 캜 and the roasting temperature exceeds 700 캜, the undrawn iron chloride crystals in the roasting furnace may be liquefied to form a molten phase with the roasted iron oxide, It is preferable that the temperature is 700 占 폚 or less.

It is preferable that the total reaction time in the roasting furnace is maintained for 60 to 90 minutes from the charge of the raw material to the discharge of the iron oxide. The reaction time is preferably about 60 to 90 minutes under the roasting conditions of the present invention, and the reaction time can be selectively adjusted according to the charging rate (filling rate) of the iron chloride crystals in the roasting furnace.

The iron chloride crystals are preferably obtained by evaporating and concentrating an aqueous solution containing chloride ions and iron ions to crystallize the iron chloride.

As an example of an aqueous solution containing the chloride ion and the iron ion, a by-product of a nickel wet smelting process for recovering nickel using an acid solution containing a chloride ion from nickel ore containing nickel and iron, .

The nickel ore is not particularly limited, and an ore including nickel and iron such as limonite, saponite and the like can be used.

The nickel wet smelting process comprises dissolving nickel from a nickel ore containing nickel and iron in a chloride ion-containing acid solution such as hydrochloric acid, precipitating with ferronickel to recover nickel, and recovering nickel from the nickel ore containing nickel chloride and iron The present invention can be applied as long as it is a process by-product.

For example, the nickel hydrometallurgical process may include the steps of reducing nickel ore, leaching iron and nickel with reduced nickel ore into an acid, precipitating nickel ions in the leaching solution by a displacement precipitation reaction, And concentrating and recovering.

First, reducing the nickel ore. The reduction is carried out using hydrogen as a reducing agent, and the type of the gas is not particularly limited as long as it is a gas containing hydrogen. When the hydrogen-containing gas is used as the reducing gas, the reduction process can be performed at a relatively low temperature as compared with the case of using carbon. In addition, nickel metal having a specific surface area of 1-100 m 2 / g can be produced with a high activity, whereby it can be easily dissolved by an acid, so that a subsequent acid leaching process can be carried out at high speed.

As such a reducing gas, a gas containing hydrogen can be used. Preferably, hydrogen can be used alone, or an inert gas can be used together. The inert gas may be included to remove oxygen other than hydrogen present in the reducing furnace during the reduction reaction. Such an inert gas is not particularly limited as long as it is not reactive, and examples thereof include helium, argon, carbon dioxide, nitrogen and the like.

Further, another example that can be used as the hydrogen-containing reducing gas includes a coke oven gas (COG) containing 50 vol% or more of hydrogen generated in the iron ore smelting process or a gas generated in a methane hydrogen reforming reaction , And hydrogen-containing LNG reforming gas containing 65 vol% or more of hydrogen.

The reduction step may be performed in a temperature range of 725-950 DEG C using hydrogen as a reducing agent to reduce metal oxides such as iron and nickel in the nickel ore. The nickel ore reduced by such a reaction can be obtained. Hereinafter, the reduced nickel ore is also referred to as 'reduction light'. For convenience, the reduction light used in the leaching step according to the process in which the reduction light is used is referred to as 'leaching reduction light', and the reduction light used in the precipitation step is referred to as 'precipitation reduction light'.

The exhaust gas obtained in the reduction step is separated and discharged. The reducing light is converted into a slurry by using water, and then an acid is added to the slurry to thereby carry out a leaching step of dissolving iron and nickel in the ore. Nickel and iron contained in the reducing material in the slurry are dissolved by the acid and leached into the ions.

As the acid which can be used in the leaching step, hydrochloric acid, sulfuric acid and the like can be used, but hydrochloric acid is preferably used for recovery of iron and acid from the waste liquid discharged after nickel precipitation.

On the other hand, the nickel ore contains Al 2 O 3 , SiO 2 , Cr 2 O 3 and the like. These components rarely dissolve by the acid in the leaching reaction step and remain mostly as solid residue, And eluted into the leach solution. However, since the Al, Si, and Cr components are elements capable of causing deterioration of precipitation efficiency of nickel in the subsequent precipitation step, it is preferable that these components are removed from the leach solution before the precipitation step.

The Al, Si and Cr components dissolved in the leaching solution can be precipitated and removed by forming a solid hydroxide by changing the pH of the leaching solution by adding an alkaline agent to the leaching solution. As a result, the precipitate filtrate becomes a sludge containing a solid-phase hydroxide, and a solid content is removed by means such as filtration to obtain an extract liquid containing no Al, Si and Cr components.

The content of the alkaline agent added to the above-mentioned leach solution is not particularly limited, but it is preferable that the pH of the leachate is adjusted to a range of 1.5 to 3.5. The pH of the precipitation filtrate obtained by the acid added during the leaching reaction has a very high acidity, usually 1 or less. By controlling the pH to the above range, the Al, Si and Cr components present in the solution can be effectively removed. However, when the pH of the precipitation filtrate exceeds 3.5, the iron ions in the solution are also converted into hydroxides, which may result in lowered iron recovery. It is more preferable that the pH does not exceed 3.5.

At this time, the alkaline agent may be added before removing the leaching residue from the leaching solution to convert the leaching residue and the hydroxide together after the conversion to the hydroxide, as well as removing the leaching residue by solid-liquid separation from the leaching solution, To form a sludge, which is then filtered to obtain a pH-controlled leach solution.

At this time, the alkaline agent to be added for controlling the pH of the above-mentioned leaching solution is not particularly limited and can be used without limitation as long as it can raise the pH of the leaching solution. For example, hydroxides of metals such as Na, K, Ca, Mg, Fe, Mn, or Ni. They may be used alone or as a mixture.

When the precipitation reducing light is supplied to the leaching solution obtained by the leaching reaction, the nickel ions in the leaching solution are replaced with the iron ions in the reducing light to precipitate into ferronickel precipitates by the reaction shown in the following formula (7) Reacts with chlorine to form iron chloride.

(Ni 0 .1 Fe 0 .9 ) Cl 2 + {(Ni 0 .1 Fe 0 .9 ) + 2 Fe} = Ni 0 .2 Fe 0 .8 + 2 Fe + 0.1 FeCl 2

Therefore, the precipitate of ferronickel can be recovered by solid-liquid separation such as filtration from the precipitation liquid containing the precipitate obtained by the precipitation reaction.

Nickel can be precipitated by the substitution reaction of the nickel ions in the leaching solution and the iron ions in the reducing light by adding the reducing light to the leaching solution thus obtained. As a result, a precipitate of the ferronicky form can be obtained, and precipitates of the ferronickel can be obtained by recovering the precipitate from the solution by solid-liquid separation.

The precipitation filtrate remaining after recovering the precipitate is an aqueous solution of iron chloride containing iron chloride, which is an aqueous solution containing chloride ions and iron ions. The iron chloride aqueous solution may be roasted to obtain iron oxide.

As described above, the alkaline agent added for adjusting the pH of the leach solution can be used without limitation. However, the Na, K, or Ca ions contained in the alkaline agent or nickel ore added to the pH of the leach solution, dissolved in the acid by the acid, react with the chloride ion in the aqueous solution of the iron chloride to produce NaCl, KCl, CaCl 2 and the like. Unlike the chlorides of other alkali agents, these chlorides such as NaCl, KCl and CaCl 2 do not undergo thermal decomposition even during the roasting process to recover iron ores and acids, so that hydrochloric acid is not recovered, It is mixed with iron oxide to increase the Cl concentration of the iron oxide product so that the quality of the iron oxide is remarkably lowered so that it can not be recycled as iron ore.

Therefore, it is necessary to prevent the chlorides of Na, K and Ca from being mixed into the iron oxide to improve the quality of the iron oxide. In order to obtain high quality iron oxide free from the incorporation of alkali chloride, the iron chloride crystals obtained from the precipitation filtrate are subjected to solid-liquid separation by filtration or the like to obtain the hydrochloride crystals from which the chlorides of Na, K and Ca have been removed, High-purity iron oxide can be obtained by roasting a ferric chloride crystal.

Specifically, in order to remove the alkali chloride present in the aqueous solution of iron chloride, the aqueous solution of iron chloride is concentrated by evaporation to the solubility of the iron chloride or higher to obtain the green colored ferric chloride crystals.

The crystallization of iron chloride can induce crystallization of iron chloride from an aqueous solution of iron chloride by heating the precipitation filtrate to high temperature to evaporate water and concentrate the precipitation filtrate. At this time, if the crystallization temperature is high, the 2-hydrate (2H 2 O) crystallizes in the state having the crystal number, and when the crystallization temperature is low as in the case of heating in the vacuum state, the 4-hydrate (4H 2 O ) (FeCl 2 .4H 2 O) can be obtained.

As described above, in the crystallization of iron chloride, steam can be used as crystallization energy by using steam evaporated during evaporation and concentration, energy can be saved, steam can be recycled by heating or pressurizing the surplus steam, Energy can be reduced.

The iron chloride is solidified by the crystallization of the iron chloride by such evaporation concentration, but most of the alkali ion present in the solution exists in the ion state. Therefore, it is possible to separate the iron chloride crystals from the precipitation filtrate by a solid-liquid separation means such as filtration. As a result, a highly pure iron chloride crystal can be obtained.

Alkali ions, particularly Na, K and Ca components, can be removed from the iron chloride crystals obtained by such a method, but alkaline ions are added to the surface of the iron chloride crystals because the alkali ions are concentrated in the solution. Therefore, it is more preferable to obtain higher quality iron oxide by removing the alkali ions adhering to the crystal surface.

In order to remove the alkali ions adhering to the surface of the iron chloride crystals, some of the adhered alkali ions can be removed from the surface of the iron chloride crystals by washing the iron chloride crystals using a saturated solution of iron chloride in which the high purity chloride is dissolved at a saturated concentration.

Iron chloride and chlorine gas can be obtained by pyrolyzing the solid phase high-purity iron chloride crystals obtained by the above-mentioned method by crystallization roasting which roasts. This can be expressed by the following equation (8).

(8) 2FeCl 2 (s) + 2H 2 O (g) + 1 / 2O 2 ? Fe 2 O 3 (s) + 4HCl (g)

The pyrolysis reaction may be performed at a temperature of 400 ° C or higher. On the other hand, the upper limit of the roasting furnace temperature can be appropriately set in accordance with the operating temperature range of the roasting furnace and the like, and is not particularly limited. However, it is preferable to set the temperature to 800 DEG C or less from the viewpoint of economical efficiency such as energy consumption required for roasting. More preferably, the temperature of the roasting furnace during roasting is preferably set within a temperature range of 500 to 700 占 폚.

On the other hand, the iron chloride crystals may be formed into iron oxide and chlorine by solution roasting in which the iron chloride crystals are dissolved in water, rehydrated and dissolved, and sprayed to a roasting furnace. However, such solution roasting is capable of pyrolyzing pyrolysis at a roasting temperature of about 600-900 ° C.

From the viewpoint of reducing the energy cost as described above, crystallization roasting is more preferable. Further, when the solution is roasted, fine iron oxide powder having a fine particle size is obtained. In this case, an additional process for pelletizing the fine powder for utilization in the industry is required, for example, by introducing the obtained iron oxide into an electric furnace. However, iron oxide obtained by crystallization roasting can be obtained in the form of granules having a large particle size, which is more preferable from the viewpoint of not requiring an additional pelletization step.

The iron oxide obtained by roasting may be recovered in the form of solid phase powder using a dust collector or the like. On the other hand, chlorine is discharged together with the flue gas in a gaseous state, and hydrochloric acid can be obtained by passing water through the flue gas.

Hereinafter, embodiments of the present invention will be described in detail. The following examples are for the purpose of understanding the present invention and are not intended to limit the present invention.

(Example 1)

In Example 1, roasting iron rods were simulated in a laboratory, and iron oxide roasting was conducted using iron chloride crystals (FeCl 2 .2H 2 O). The process conditions are shown in Table 1, and the results are shown in Table 1 .

No. Amount of iron chloride crystals (g) Amount of water vapor (%) Air-fuel ratio Roasting temperature (℃) Roasting time (minute) result compare One 15 96 One 600 60 US rosy Comparative Example 1 2 15 128 One 600 60 US rosy Comparative Example 2 3 15 160 One 600 60 US rosy Comparative Example 3 4 15 205 One 600 60 US rosy Comparative Example 4 5 5 55 1.5 600 60 Good Inventory 1 6 15 32 1.5 600 60 Fume generation Comparative Example 5 7 15 50 1.6 600 60 Good Inventory 2 8 15 50 1.8 600 60 Good Inventory 3 9 15 64 1.4 600 60 Good Honorable 4 10 15 64 1.6 600 60 Good Inventory 5 11 15 64 1.8 600 60 Good Inventory 6 12 15 64 2 600 60 Good Honorable 7 13 15 64 1.6 650 30 US rosy Comparative Example 6 14 15 64 1.8 650 30 US rosy Comparative Example 7 15 15 64 2 650 30 US rosy Comparative Example 8

(In Table 1, the amount of steam is the weight of the iron chloride crystals to be added, and the air-fuel ratio means the air ratio in the case of using LNG as fuel)

As shown in Table 1, when the conditions of the present invention were satisfied, it was confirmed that the roasting was stable.

On the other hand, in Comparative Examples 1 to 4, it was confirmed that the amount of steam injected was excessive relative to the fuel, and the air-fuel ratio did not exceed the present invention, and sufficient roasting was not achieved due to the absence of reactive oxygen. On the other hand, in the case of Comparative Example 5, there was a problem that fume due to side reaction occurred because the amount of water vapor input was too small.

On the other hand, in the case of Comparative Examples 6 to 8, sufficient roasting did not proceed due to the reaction for 30 minutes during roasting, and it was confirmed that roasting was caused.

(Example 2)

In Example 2, the charging amount of iron chloride crystals per hour was set at 220 kg / hr in a pilot condition, the amount of water vapor was maintained at 66 kg / hr (about 30% of fuel weight), and the air- To maintain 1.4, and the roasting temperature was maintained at 600 캜.

The oxide components thus obtained were analyzed and the results are shown in Table 2 below.

division Fe Ca Mg Mn Si Al Cl Oxide 1 69.0 0.015 0.58 1.36 0.012 <0.005 0.076 Oxide 2 69.1 0.016 0.61 1.37 0.012 <0.005 0.059 Oxide 3 68.7 0.013 0.51 1.24 0.014 <0.005 0.061 Oxide 4 69.0 0.012 0.46 1.28 0.011 <0.005 0.064

(The content of each component in the above Table 2 represents the content of the alloy contained in the oxide in terms of% by weight)

According to the method for producing iron oxide of the present invention, it was confirmed that iron oxide was obtained at a recovery rate of about 86% of the iron oxide contained in the iron chloride. It was confirmed that the dust was trapped in the dust collecting device by scattering about 14% of the iron oxide and the loss was very small.

Claims (8)

Preparing a ferric chloride crystal; And
Roasting the iron chloride crystals in a roasting furnace to form iron oxide,
Wherein the steam is introduced into the roasting furnace at a rate of 40 to 70% of the weight of the raw material introduced into the roasting furnace.
delete The method according to claim 1,
Wherein the air-fuel ratio of the combustion burner used in the roasting furnace is 1.4 to 2.4.
The method according to claim 1,
Wherein the temperature of the roasting furnace is 500 to 700 占 폚.
The method according to claim 1,
Wherein the total reaction time in the roasting furnace is maintained for 60 to 90 minutes from the loading of raw materials to the release of iron oxide.
The method according to claim 1,
Wherein the iron chloride crystals are obtained by evaporating and concentrating an aqueous solution containing chloride ion and iron ion to crystallize the iron chloride.
The method of claim 6,
Wherein said aqueous solution is obtained as a by-product of a nickel wet smelting process for recovering nickel using an acid solution containing chloride ions from nickel ore containing nickel and iron.
The method of claim 7,
The nickel wet smelting process may comprise:
Reducing the nickel ore;
Leaching iron and nickel with reduced nickel ore into an acid to obtain an extract;
Precipitating nickel ions of the leach solution by a displacement precipitation reaction; And
And concentrating and recovering the nickel.
KR1020150185815A 2015-12-24 2015-12-24 Method for manufacturing iron oxide KR101798731B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200051233A (en) * 2018-11-05 2020-05-13 주식회사 포스코 Manufacturing method of cylindrical porous iron powder

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000001318A (en) 1998-06-11 2000-01-07 Kawasaki Steel Corp Calcination furnace for iron chloride aqueous solution
JP2000344526A (en) 1999-06-02 2000-12-12 Kawasaki Steel Corp Roasting furnace for producing iron oxide, and production of iron oxide
JP2005145757A (en) * 2003-11-14 2005-06-09 Nisshin Steel Co Ltd Method for manufacturing iron oxide powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000001318A (en) 1998-06-11 2000-01-07 Kawasaki Steel Corp Calcination furnace for iron chloride aqueous solution
JP2000344526A (en) 1999-06-02 2000-12-12 Kawasaki Steel Corp Roasting furnace for producing iron oxide, and production of iron oxide
JP2005145757A (en) * 2003-11-14 2005-06-09 Nisshin Steel Co Ltd Method for manufacturing iron oxide powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200051233A (en) * 2018-11-05 2020-05-13 주식회사 포스코 Manufacturing method of cylindrical porous iron powder
WO2020096293A1 (en) * 2018-11-05 2020-05-14 주식회사 포스코 Method for manufacturing needle-shaped or rod-shaped porous iron powder and needle-shaped or rod-shaped porous iron powder manufactured thereby
KR102175428B1 (en) * 2018-11-05 2020-11-06 주식회사 포스코 Manufacturing method of cylindrical porous iron powder

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