KR101798731B1 - Method for manufacturing iron oxide - Google Patents
Method for manufacturing iron oxide Download PDFInfo
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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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- South Korea
- Prior art keywords
- iron
- nickel
- roasting
- chloride
- iron oxide
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 82
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- 229910052759 nickel Inorganic materials 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 31
- 238000002386 leaching Methods 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- -1 iron ion Chemical class 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000001805 chlorine compounds Chemical class 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910000863 Ferronickel Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
Landscapes
- 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
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 .
(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.
(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)
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.
Wherein the air-fuel ratio of the combustion burner used in the roasting furnace is 1.4 to 2.4.
Wherein the temperature of the roasting furnace is 500 to 700 占 폚.
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.
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.
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 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.
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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 |
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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 |
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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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