WO2018117771A1 - Procédé de récupération de nickel et de cobalt à partir de matière première contenant du nickel, du fer et du cobalt - Google Patents

Procédé de récupération de nickel et de cobalt à partir de matière première contenant du nickel, du fer et du cobalt Download PDF

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WO2018117771A1
WO2018117771A1 PCT/KR2017/015416 KR2017015416W WO2018117771A1 WO 2018117771 A1 WO2018117771 A1 WO 2018117771A1 KR 2017015416 W KR2017015416 W KR 2017015416W WO 2018117771 A1 WO2018117771 A1 WO 2018117771A1
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Prior art keywords
nickel
iron
cobalt
solution
precipitation
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PCT/KR2017/015416
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English (en)
Korean (ko)
Inventor
이병필
한길수
박진균
이재영
엄형섭
조성구
이창규
김용찬
김덕
이고기
Original Assignee
주식회사 포스코
재단법인 포항산업과학연구원
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Priority claimed from KR1020170145279A external-priority patent/KR101949042B1/ko
Application filed by 주식회사 포스코, 재단법인 포항산업과학연구원 filed Critical 주식회사 포스코
Priority to CN201780079842.2A priority Critical patent/CN110114482B/zh
Priority to EP17882514.7A priority patent/EP3561090A4/fr
Priority to AU2017380307A priority patent/AU2017380307B2/en
Priority to US16/472,479 priority patent/US20210130926A1/en
Publication of WO2018117771A1 publication Critical patent/WO2018117771A1/fr
Priority to PH12019501436A priority patent/PH12019501436A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/06—Refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases

Definitions

  • the present invention relates to a process for recovering nickel and cobalt from nickel, iron and cobalt containing raw materials.
  • Ore containing nickel and iron is laterite (Laterite), which is a nickel oxide ore, and may be classified into limonite, saprolite, and the like according to the mineral phase. These ores are passivated and therefore resistant to acids, resulting in slow dissolution reactions to acids. Therefore, as a method for effectively leaching nickel, methods for recovering nickel by dissolving it in an acid in an autoclave under high temperature and high pressure have been proposed, which is called 'HPAL (High Pressure Acid Leaching)'.
  • 'HPAL High Pressure Acid Leaching
  • the nickel recovery rate does not exceed 85% even after leaching for several months or more.
  • the HPAL method enables the leaching of 90% or more of nickel within two hours. It can be called a method.
  • patent documents 1 and 2 are mentioned.
  • HPAL method should be carried out under the high temperature and high pressure of the autoclave, and it is known that it can be mainly used only for the titanium material due to its strong acidity, and thus has the disadvantage of very high equipment cost and high maintenance cost.
  • a caustic soda which is an expensive precipitant, or an environmentally harmful precipitant such as H 2 S must be used for nickel concentration, there is also a problem in that a facility cost for treating this is increased.
  • leaching limonite nickel ore using the above method high-speed leaching is possible, but limonite ore has a high iron content and a low nickel content, and when leaching nickel by acid dissolution, iron is leached relatively.
  • nickel is leached in small amounts, there is a problem that it is difficult to separate iron and nickel from the leach.
  • Patent Documents 3 and 4 disclose methods for effectively concentrating nickel by recovering nickel and iron from ore with low nickel quality and recovering ferronickel from these concentrates
  • Patent Document 5 discloses a process by-product. A method of improving the nickel content of a nickel concentrate after precipitation by using the obtained roasted iron ore as a slurry for precipitation after reduction is disclosed.
  • Patent Document 1 Korean Unexamined Patent Publication No. 10-2007-7020915
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2010-031341
  • Patent Document 3 Korean Registered Patent No. 10-1353721
  • Patent Document 4 Korean Registered Patent No. 10-1359179
  • Patent Document 5 Korean Registered Patent No. 10-1657810
  • the present invention has been made to solve the above problems, and an object thereof is to provide a method for efficiently recovering nickel and cobalt from a raw material containing nickel, iron, and cobalt.
  • the step of reducing the raw material containing nickel, iron and cobalt to a reducing gas containing hydrogen Adding acid to the reduced raw material and leaching to obtain a solution containing nickel, iron and cobalt ions; Preparing a purified solution from which impurities are removed by adding a hydroxide containing iron or magnesium to the solution; Depositing nickel and cobalt by administering reduced iron for precipitation to the tablet solution containing nickel and cobalt ions; Adding an acid to the precipitate obtained in the precipitation step and leaching to obtain a solution containing nickel, iron and cobalt ions; Adding an alkaline agent to the nickel, cobalt and iron-containing solution and oxidizing with a gas containing oxygen to remove iron; And adding an alkali agent to the solution to obtain nickel and cobalt hydroxides.
  • the amount of the reduced iron for precipitation may be 1.5 to 2.5 times the molar sum of nickel and cobalt ions present according to the following relational formula.
  • the reduced iron for precipitation may be obtained by indirectly reducing the iron chloride roasted iron ore obtained from the by-product of the nickel smelting process with solid carbon or reducing gas.
  • the reduction rate of the reduced iron for precipitation may be 80 to 99%.
  • a particle size of the reduced iron for precipitation may be 5 ⁇ m or less.
  • the reduction temperature may be 500 ⁇ 950 °C.
  • the reduction temperature may be 500 ⁇ 950 °C.
  • the iron chloride roast iron ore is obtained by evaporating and concentrating a solution containing iron and chlorine ions generated as a filtrate in the nickel smelting process to obtain a concentrated solution; Crystallizing the concentrated solution to obtain iron chloride crystals; Solid-liquid separation of the iron chloride crystals and the slurry; And roasting the iron chloride crystals to obtain iron chloride roasted iron ore.
  • the acid introduced into the reduced raw material may be a precipitated filtered filtrate with an ion exchange resin to recover residual nickel and cobalt, and the ion exchange resin may be stripped with an acid to include an acid containing nickel and cobalt. have.
  • Acids containing nickel and cobalt obtained by the ion exchange may be re-introduced into the leaching process.
  • the alkaline agent may be at least one selected from calcium hydroxide or calcium carbonate.
  • the nickel and cobalt hydroxides may be leached into sulfuric acid and solvent extracted to prepare nickel sulfate and cobalt sulfate.
  • the chlorine component and calcium component in the leachate may be removed in the form of calcium chloride.
  • valuable metals such as nickel, cobalt, and the like can be recovered from a raw material containing nickel, iron, and cobalt.
  • the nickel concentration is low
  • the iron concentration is high
  • iron is relatively high when leaching nickel. While leached, nickel may be more suitably applied in the case of small leaching, which makes it difficult to separate iron and nickel.
  • Figure 1 schematically shows a flow chart of the nickel and cobalt recovery method according to an embodiment of the present invention.
  • the present invention relates to a method for producing a high concentration of nickel concentrate from nickel, iron and cobalt-containing raw material, according to one aspect, reducing the raw material containing nickel, iron and cobalt with a reducing gas containing hydrogen; Adding acid to the reduced raw material and leaching to obtain a solution containing nickel, iron and cobalt ions; Preparing a purified solution from which impurities are removed by adding a hydroxide containing iron or magnesium to the solution; Depositing nickel and cobalt by administering reduced iron for precipitation to the tablet solution containing nickel and cobalt ions; Adding an acid to the precipitate obtained in the precipitation step and leaching to obtain a solution containing nickel, iron and cobalt ions; Adding an alkaline agent to the nickel, cobalt and iron-containing solution and oxidizing with a gas containing oxygen to remove iron; And adding an alkali agent to the solution to obtain nickel and cobalt hydroxides.
  • the nickel iron-containing raw material to which the present invention can be applied is not particularly limited, and may be applied as long as it contains nickel and iron, and preferably nickel ore, for example, nickel ore such as limonite and sapolite Can be mentioned.
  • Nickel ore varies depending on the type of ore, but usually contains 1-2.5% Ni and 15-55% Fe.
  • limonite ore has a low nickel concentration of 1-1.8% and an iron concentration of 30-55. High in% The present invention can be effectively applied even in recovering nickel from such relatively low nickel content of limonite.
  • a method for producing a nickel concentrate from the nickel, iron and cobalt-containing raw materials of the present invention will be described in detail.
  • the nickel, iron, and cobalt-containing raw materials can be effectively reduced in the reduction step, and may be subjected to a pretreatment step as necessary.
  • This pretreatment process includes drying, grinding and firing steps.
  • Nickel, iron, and cobalt-containing raw materials typically contain about 20-40% adhered water and about 10% crystalline water. In the state containing such adhering water, the grinding efficiency is lowered, and when the nickel iron-containing raw material is fired and then pulverized, there is a risk of causing a load on the grinding equipment due to high heat. Therefore, it is preferable to dry a nickel iron containing raw material before grind
  • the particle size is preferably 1 mm or less. Pulverizing the particle size to 1 mm or less is preferable for reducing and leaching efficiency improvement.
  • the lower limit of the particle size is not particularly limited, but is preferably 10 ⁇ m or more for the efficiency of the grinding step.
  • the crystal water may not be removed in the drying process, and may cause a decrease in the reaction efficiency in the reduction reaction.
  • the calcining treatment may be performed in a range of 250 to 850 ° C. depending on the kind of ore.
  • the nickel, iron, and cobalt-containing raw materials are reduced to obtain nickel, iron, and cobalt-containing raw materials.
  • the reduction can be performed at a temperature range of 550 to 950 ° C. using a reducing gas containing hydrogen as the reducing agent.
  • the reduction temperature is less than 550 ° C, the reduction is not sufficient, the recovery rate during subsequent leaching is low, the precipitation efficiency may also be lowered. As the reduction temperature is increased, the leaching yield and precipitation efficiency may be increased. However, when the reduction temperature is increased, additional reduction efficiency may not be increased, and workability due to intergranular sintering may be reduced.
  • CO gas may be used instead of hydrogen, but should be reduced at a high temperature of 1000 ° C. or higher, and the activity of the powder reduced at high temperature is lowered, thereby lowering the leaching rate and further lowering the precipitation efficiency.
  • the reducing gas may be a gas containing hydrogen, hydrogen may be used alone, and inert gas may be used together. Helium, argon, carbon dioxide, nitrogen, etc. are mentioned as said inert gas.
  • Other examples that can be used as the hydrogen-containing reducing gas include Cokes Oven Gas (COG) containing 50% or more of hydrogen generated in an iron ore smelting process, or gas generated in a methane hydrogen reforming reaction. And hydrogen-containing LNG reformed gas containing 65% or more.
  • COG Cokes Oven Gas
  • Hydrogen contained in the reducing gas is reduced by reacting with oxygen of nickel and iron present in an oxidized state in nickel, iron and cobalt-containing raw materials to generate water.
  • oxygen of nickel and iron present in an oxidized state in nickel, iron and cobalt-containing raw materials is shown in the following formula (1).
  • the amount of hydrogen included in the reducing gas may be added in excess of the theoretical equivalent ratio for efficient reduction reaction. However, in consideration of the increase in the process cost, it may be included in the number of moles of 1 to 5 times, 2 to 5 times or 2 to 4 times the theoretical equivalent ratio.
  • the nickel, iron, and cobalt-containing raw materials reduced by such a reaction can be obtained, and hydrogen which has not participated in the reaction of the added hydrogen can be recovered and re-introduced into the process.
  • acid is added to the slurry to dissolve and leach nickel, iron, and cobalt contained in the reducing material in the slurry, so that nickel is nickel ions, iron is iron ions, and cobalt is cobalt. Ionize with ions.
  • leaching acid hydrochloric acid or sulfuric acid may be used.
  • the acid is an acid obtained by treating the filtered filtrate after the precipitation step described below with an ion exchange resin to recover residual nickel and cobalt, and removing the resin with an acid to mix an acid containing nickel and cobalt with a leaching acid.
  • the ion exchange resin may be typically bis-picolylamine (Bis-picolylamine), in addition to the resin that selectively adsorbs nickel and cobalt may be used.
  • an acid containing nickel and cobalt with the leaching acid to dissolve the nickel and iron cobalt, the nickel and cobalt filtered without precipitation in the precipitation step may be further recovered.
  • hydrochloric acid In order to leach such reducing raw materials into an acid, when hydrochloric acid is used as the acid, hydrochloric acid must be added at a molar number not less than twice the number of moles of (Fe + Ni) as shown in the above formula (2). However, when adding hydrochloric acid more than four times the number of moles of (Fe + Ni), no further leaching efficiency improvement is obtained. Therefore, it is preferable to add in the range of two times to four times the number of moles of (Fe + Ni). Do.
  • oxides such as Al 2 O 3 , SiO 2 , and Cr 2 O 3 contained in nickel, cobalt, and iron-containing raw materials hardly occur by acid, and remain as solid residues, but some are dissolved by acid. And elutes into the leach solution.
  • Eluted Al, Si, Cr, and the like are elements that may degrade the precipitation ability and the quality of nickel, cobalt and iron precipitates in the subsequent precipitation step, it is preferable to remove before the precipitation step.
  • Elements such as Al, Si, Cr, and the like dissolved in the leach liquor can be removed by precipitation with a solid hydroxide by adding an alkaline agent to the leach liquor to change the pH of the leach liquor.
  • the alkali agent added for adjusting the pH of the leaching solution is not particularly limited, and may be used without limitation as long as it can increase the pH of the leaching solution.
  • hydroxides of metals such as Ca, Mg, Fe, and Ni
  • oxides such as CaO and MgO may be used alone or in combination.
  • the quantity of the alkaline agent added to a leach liquid is not specifically limited, It is preferable to add to the extent which can adjust pH of a leach liquid to the range of 1.5-3.5.
  • the pH of the leaching solution is generally high in acidity of 1 or less by the added acid, and when the pH is adjusted in the above range, impurities such as Al, Si, Cr, etc. in the solution are effectively precipitated as hydroxides.
  • the pH exceeds 3.5 when the alkaline agent is added nickel, cobalt, and iron in the solution may precipitate out of the hydroxide, thereby reducing the recovery rate.
  • the alkali agent added for adjusting the pH of the leachate is not particularly limited and may be used without limitation as long as the pH of the leachate may be increased.
  • hydroxides of metals such as Ca, Mg, Fe, and Ni and oxides such as CaO and MgO may be used alone or in combination.
  • the solid residue precipitated as described above is very easy to be separated by filtration, so that a leaching solution containing nickel, cobalt, iron, and ions can be obtained by separating with a solid-liquid separator such as a filter press or a decanter.
  • a solid-liquid separator such as a filter press or a decanter.
  • Precipitating nickel and cobalt by administering reduced iron for precipitation to the tablet solution containing nickel and cobalt ions.
  • the concentrated nickel, iron and cobalt ions are precipitated into a nickel concentrate.
  • reduced iron which is indirectly reduced by solid carbon or a reducing gas, is used as a seed material for precipitation, and may be preferably in powder form.
  • the principle of the substitution reaction as described above is due to the natural potential difference between iron, nickel and cobalt, and the battery is formed by the natural potential difference between the iron in the iron and nickel ion-containing solution and the iron in the precipitated iron powder.
  • the dissolution reaction by oxidation is progressed, and the reaction in which nickel ions in the iron and nickel ion-containing solution are reduced and precipitated at the negative electrode site proceeds.
  • the reaction proceeds by a mechanism such as cobalt and railroad, and a reaction in which cobalt ions are reduced and precipitated proceeds.
  • the reduced iron for precipitation requires very high activity to enable efficient precipitation recovery of nickel.
  • Reduced iron having such a high activity can be obtained by reducing the iron oxide obtained by roasting the iron chloride crystals in the process at 700 to 900 °C hydrogen.
  • iron chloride roast iron ore obtained from the by-product of the nickel smelting process can be directly reduced with solid carbon or reducing gas to obtain reduced iron for precipitation.
  • the iron chloride roasted iron ore may be obtained from a solution containing iron and chlorine ions generated as a filtrate in a nickel smelting process for recovering nickel using a hydrochloric acid solution from a nickel ore containing nickel and iron.
  • An example of a process for obtaining iron chloride roasted iron ore used in the present invention is as follows. Obtaining a concentrated solution by evaporating and concentrating a solution containing iron and chlorine ions generated as a filtrate in a nickel smelting process of recovering nickel using a hydrochloric acid solution from a nickel ore containing nickel and iron; Crystallizing the concentrated solution to obtain iron chloride crystals; Solid-liquid separation of the iron chloride crystals and the slurry; It may be obtained by a process comprising the step of roasting the iron chloride crystals to obtain iron chloride roasted iron ore.
  • the iron ion and chloride ion containing solution can be obtained by the following process. That is, a leaching step of dissolving nickel ore containing nickel and iron with hydrochloric acid to obtain a leaching solution in which nickel and iron ions are leached; PH adjustment step of adjusting the pH by adding an alkali agent to the leaching solution, and solid-liquid separation of the solid phase impurities in the leaching solution; Adding nickel ore containing nickel and iron to the leaching solution and then depositing nickel with ferronickel; And it may be a filtrate generated in the nickel smelting process comprising a precipitate recovery step of filtering and recovering the solid precipitate by solid-liquid separation from the precipitate.
  • a temperature of 500 ⁇ 950 °C is preferred. If the reduction temperature is less than 500 ° C, Fe 2 O 3, which is the Fe oxide of roasted iron ore, does not go through FeO, which is a reducing intermediate phase, and has a long reduction time due to kinetic problems such as reduction from Fe 3 O 4 to Fe. When the temperature is higher than 950 ° C, reduction occurs, so that Fe, which is reduced to an excessive temperature, is sintered or energy is excessive.
  • the reducing gas a gas containing hydrogen, CO, or a mixed gas thereof, or at least one of hydrogen and CO may be used.
  • the reducing gas may be 100% hydrogen or 100% CO or mixed gas such as hydrogen and CO mixed gas or hydrogen + CO + LNG reforming gas or COG.
  • the reduction temperature is preferably 700 to 1200 ° C. If the reduction temperature is less than 700 °C there is a problem that takes a long reduction rate, if the 1200 °C or more, reduced Fe is sintered or excessive energy takes a problem in terms of economics. Coal, coke, or the like may be used as the solid carbon.
  • the precipitated reduced iron may contain 5 wt% or less of elements such as Fe, Ni, Mg, Si, and Al, and preferably 3 wt% or less.
  • the precipitation-reduced iron for reducing is Fe: 58 ⁇ 72% by weight, Ni: 1% by weight or less, the total content of Mg, Si and Al: 5% by weight or less, preferably 3% by weight or less, the rest is oxygen and It may contain other impurities.
  • the reduction rate of the reduced roasted roast iron is preferably 80 to 99%.
  • the reduction rate is less than 80%, it is easy to secure a deposition rate of Ni of 97% or more in the precipitation process, but the Ni content of the Ni concentrate after precipitation is low due to the high content of impurities such as unreduced oxygen in the precipitation roasting iron.
  • impurities such as unreduced oxygen in the precipitation roasting iron.
  • the cost of the process increases.
  • the reduction rate exceeds 99% there is a low impurity advantage, but after the reduction, the metal Fe in the roasting metal for reduction after precipitation has a disadvantage in that the precipitation rate is reduced due to the large particle size due to sintering, etc., and also 95% considering the additional reduction cost High reduction rates in excess of are undesirable.
  • the average particle size of the said roasting reduced iron is 5 micrometers or less.
  • the reason for limiting the particle size of the precipitated roasted reduced iron is to increase the specific surface area for the smooth reaction of the metal Fe in the precipitated roasted reduced iron in the solution and Ni ions in the leached solution during the precipitation process. Particle size can be controlled through a general dry / wet crushing process.
  • iron oxide obtained from the iron chloride crystals if the specific surface area, etc. is high, iron oxide or reduced iron having high activity after reduction may be applied to the present invention.
  • the amount of reduced iron used for precipitation added to the iron, nickel, and cobalt ion-containing solution to reduce the nickel and cobalt may be adjusted according to the amount of the reduced raw material used for leaching, and the use ratio of the iron powder may be precipitated. It is very important as a factor in determining the recovery rate and the nickel concentration of the final product obtained and the ratio of iron and nickel.
  • the input amount of the reduced iron for precipitation is input differently according to the amount of nickel in the iron and nickel ion-containing solution, and in order to satisfy the nickel recovery rate of 95% or more, the input amount defined by the following Equation 1 is 1.5 to 2.5 times by weight. It is desirable to satisfy.
  • Seed ratio (Fe content in reduced iron for precipitation) / (Ni + Co ion content in leaching solution)
  • Equation 1 is a formula defining the amount of the iron powder for precipitation in consideration of the content of nickel and cobalt in the solution to be precipitated, the metal iron in the reduced iron for precipitation of the formula (4) and (5) and leaching In consideration of the precipitation reaction of the nickel ions in the solution, it is preferable to add a reduced iron for precipitation containing 1.5 to 2.5 times the metal iron of nickel and cobalt content in the leaching solution.
  • the amount of precipitated iron powder is small, so that the nickel content of the nickel concentrate after precipitation is very high such that 40% or more is possible, but there is a possibility that nickel ions which do not participate in the precipitation reaction in solution may exist. It is not good in terms of recovery rate, and when it is 2.5 times or more, a high recovery rate of nickel can be as high as 99%. However, the nickel content in the nickel concentrate after precipitation is so low that additional costs increase such as iron removal in subsequent processes. .
  • acid is added to dissolve and releach nickel, cobalt and iron precipitates so that nickel is ionized to nickel ions, cobalt to cobalt ions and iron to iron ions.
  • the acid used in the acid leaching step is not particularly limited, but hydrochloric acid or sulfuric acid may be used.
  • the reaction is performed as shown in the following formulas (6) and (7) so that nickel, cobalt, and iron in the nickel, cobalt, and iron precipitates are added to the acid. And are leached with nickel, cobalt and iron ions, respectively.
  • the method for removing iron from the acid leaching solution containing nickel, cobalt and iron obtained through the releaching is accompanied by the following oxidation and reduction reactions. That is, the present invention comprises a step of that accompanying the oxidation precipitation, neutralization and precipitation of a solid precipitate such as FeOOH process and Fe 3 + ions for the oxidation of Fe 2 + ions Fe 3 + ions, such as below scheme .
  • the input of oxygen can be obtained by the input of air as well as pure oxygen.
  • the addition of the oxygen is preferably carried out at a rate of 0.01 L / min to 0.2 L / min per 1 L of leaching liquor, when the air is introduced at a rate of 2 to 10 times the input rate It is preferable.
  • the input of air may be performed at a rate of 0.02 L / min to 2 L / min per 1 L of leachate.
  • the feed rate of oxygen and air is less than the above range, the Fe 2 + ions Fe 3 + ion process is oxidized to be insufficiently performed, and, if the feed rate of oxygen and air exceeds the above range, the oxygen and air Since the consumption of is increased, it is not preferable in terms of cost.
  • the bubble refinement method is not particularly limited and may be achieved by, for example, using a microbubble generator.
  • a microbubble generator There are many types of microbubble generators, such as spiral liquid flow type, venturi type, ejector type, and pressurized dissolution type. In the present invention, any one may be used.
  • the temperature of the acid leaching solution is preferably maintained at 40 to 99 °C, if less than 40 °C there is a problem that the reaction rate is lowered, if it exceeds 99 °C water is evaporated there is a problem that the energy consumption increases.
  • the neutralizing agent in the form of a solid powder is preferably mixed with water to be added in the form of a slurry, and the neutralizing agent is preferably mixed with 1 to 10 times the weight of water based on the weight of the neutralizing agent.
  • the neutralizing agent may be a Ca-based neutralizer, Mg-based neutralizer or a mixture thereof, wherein the Ca-based neutralizer is, for example, at least one selected from the group consisting of limestone, CaCO 3 , CaO and Ca (OH) 2 .
  • the Mg-based neutralizing agent may be at least one selected from the group consisting of magnesite, MgCO 3 , MgO and Mg (OH) 2 .
  • Fe 3 + ions are precipitated in a solid form by the neutralizer, and there is a possibility that Ni and Co are co-precipitated with Fe, and the higher the pH of the solution, the greater the coprecipitation loss.
  • keeping the pH low to minimize Ni and Co losses reduces the rate of decarburization and lowers productivity, so it is very important in terms of Ni / Co loss and productivity that the pH remains within the appropriate range during decarburization.
  • the step of depositing the oxidized Fe 3 + ions as a solid by adding the neutralizing agent is preferably maintained at a pH of 2 to 4, when the pH is less than 2 to reduce the iron removal rate to lower the productivity If the pH exceeds 4, the coprecipitation loss in which Ni and Co are co-precipitated with Fe increases.
  • the neutralizing agent is added as soon as the supply rate than the oxidation rate of the ion of Fe 2 + Fe 3 + ions OH - ions will be the loss of Ni and Co increases, so to increase the pH of the solution.
  • the neutralizer input rate is lower than the oxidation rate, the pH of the solution is decreased, but the overall decarburization rate is decreased.
  • the neutralizing agent may be added at a rate of 0.05g / min to 0.2g / min per 1L of leachate.
  • the Fe concentration in the solution is 1 mol
  • 1 mol of CaCO 3 is added.
  • the decarburization rate may be significantly lowered, it is preferable to remove most of Fe by oxidative precipitation using oxygen and to remove a small amount of Fe with fast fruit, NaOCl, and the like.
  • a small amount of remaining Fe can be removed by other methods such as solvent extraction in the post-stage process, it is not necessary to use fruit or NaOCl.
  • Nickel and cobalt in the nickel-free and cobalt-containing solution from which the iron is removed are preferably manufactured from a solid hydroxide for commercialization.
  • Nickel and cobalt dissolved in the nickel and cobalt-containing solution may be precipitated as a solid hydroxide by changing the pH of the nickel and cobalt-containing solution in the same manner as the method of removing impurities such as Al, Si, and Cr in the leach solution.
  • the alkali agent to be added to the nickel and cobalt-containing solution is not particularly limited, but is preferably added to the extent that the pH of the nickel and cobalt-containing solution can be adjusted in the range of 8 to 10.
  • the pH of the nickel and cobalt-containing solution is usually 2 to 4 by adding an alkalizing agent, which is a neutralizing agent, while removing iron.
  • an alkalizing agent which is a neutralizing agent
  • nickel and cobalt in the solution are effectively precipitated as hydroxides of Ni (OH) 2 and Co (OH) 2, respectively.
  • the alkali agent added for adjusting the pH of the leachate is not particularly limited and may be used without limitation as long as the pH of the leachate may be increased.
  • hydroxides of metals such as Ca, Mg, Fe, and Ni and oxides such as CaO and MgO may be used alone or in combination.
  • the precipitated solid nickel and cobalt hydroxides are very easy to be separated by filtration, and the nickel and cobalt hydroxide solid phases can be obtained by separating them with a solid-liquid separator such as a filter press or a decanter.
  • the obtained nickel and cobalt hydroxides can then be manufactured in various products such as nickel, cobalt metal, nickel, cobalt sulfate, nickel, cobalt chloride, etc. according to a target wet product, a reduction process, and the like.
  • nickel and cobalt hydroxides may be leached with sulfuric acid to purify trace impurities by known techniques such as solvent extraction, and nickel and cobalt sulfates of NiSO 4 and CoSO 4 may be prepared through evaporation crystals, respectively. It can be used as a raw material.
  • nickel and cobalt hydroxides may be calcined at 600 ° C. or higher to prepare nickel and cobalt oxides such as NiO and CoO, respectively, and then reduced to a reducing agent such as hydrogen, carbon monoxide, or coal, thereby producing nickel and cobalt metals, respectively.
  • a reducing agent such as hydrogen, carbon monoxide, or coal
  • Limonite ore having the composition shown in Table 1 was dried in a rotary kiln furnace at 150 ° C. for 30 minutes, and then pulverized using a super mill to obtain a powder having an average particle size of about 15 ⁇ m.
  • the powder obtained was calcined in a calcination furnace maintained at 700 to 800 ° C. for 1 hour to remove crystal water from the ore powder.
  • the calcined nickel ore was discharged from the kiln and introduced into a rotary kiln reduction furnace cut off of oxygen, and then the ore was used at 850 ° C. using twice the number of moles of hydrogen relative to the number of moles of (Ni + Fe) contained in the prepared ore powder.
  • Reduced ore was prepared by reducing.
  • the components of the reduced ore obtained by such reduction are shown in Table 1 below. In Table 1, the content of each component represents weight%, and the balance is oxygen and trace amounts of Cr, Mn, and the like.
  • the reduced ore prepared as described above was cooled in an anoxic tank filled with nitrogen gas, and then 150 ml of water was added to 150 g of the reduced ore to prepare a slurry.
  • iron and chlorine ion-containing solutions which are by-products of the nickel smelting process, were evaporated and crystallized at a temperature of 80 and 1 atm to obtain iron chloride crystals, and then solid-liquid separation was carried out. Ready.
  • the composition of the iron oxide is shown in Table 2 below.
  • Iron oxide having a composition of Table 2 was indirectly reduced under the conditions of Table 3 to prepare reduced iron for precipitation.
  • Table 4 also shows the composition of the conventional reduced ore.
  • the content of each component represents weight percent, and the balance is oxygen and trace amounts of Cu, Zn, and the like.
  • the precipitated reduced iron and precipitation minerals prepared as described above were added to the leach solution to carry out the substitution precipitation reaction of nickel, cobalt and iron precipitates.
  • the amount of the reduced iron for precipitation and the reduced ore for precipitation are shown in Table 5 below.
  • Precipitation rate (%) ⁇ (metal content of leachate-metal content of solution after precipitation) / (metal content of leachate) ⁇ ⁇ 100
  • the Ni concentrate of Comparative Examples 1 and 2 outside the conditions of the present invention does not contain 20%, the precipitation rate is also low, having a high Ni, Co content as in the present invention Difficult to secure precipitates
  • the nickel, cobalt and iron precipitates obtained above were leached with hydrochloric acid and iron was removed using CaCO 3 and oxygen as neutralizing agents. As shown in Table 6, the recovery of each element in the leaching process was more than 99%, the iron removal rate in the subsequent de-ironing process can secure more than 99.9%.
  • the iron obtained above was removed, and alkali was added to the obtained nickel and cobalt solutions to prepare nickel and cobalt hydroxides.
  • Table 7 shows the recovery rate of both nickel and cobalt hydroxides was 99.99% or more.

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Abstract

La présente invention concerne un procédé de récupération de nickel et de cobalt à partir d'une matière première contenant du nickel, du fer et du cobalt. Selon la présente invention, des concentrations élevées en métaux précieux, tels que le nickel et le cobalt, peuvent être récupérées à partir d'une matière première contenant du nickel, du fer et du cobalt, et en particulier, les concentrations en nickel et de cobalt sont faibles et la concentration en fer est élevée, et ainsi lorsque le nickel est lixivié, une quantité relativement importante de fer est lixiviée, alors qu'une petite quantité de nickel est lixiviée. Par conséquent, la présente invention peut être appliquée de manière plus appropriée dans la fusion de minerai de nickel dans laquelle la séparation du fer et du nickel est difficile.
PCT/KR2017/015416 2016-12-23 2017-12-22 Procédé de récupération de nickel et de cobalt à partir de matière première contenant du nickel, du fer et du cobalt WO2018117771A1 (fr)

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CN201780079842.2A CN110114482B (zh) 2016-12-23 2017-12-22 用于从含有镍、铁和钴的原料中回收镍和钴的方法
EP17882514.7A EP3561090A4 (fr) 2016-12-23 2017-12-22 Procédé de récupération de nickel et de cobalt à partir de matière première contenant du nickel, du fer et du cobalt
AU2017380307A AU2017380307B2 (en) 2016-12-23 2017-12-22 Method for recovering nickel and cobalt from nickel, iron, and cobalt-containing raw material
US16/472,479 US20210130926A1 (en) 2016-12-23 2017-12-22 Method for recovering nickel and cobalt from nickel, iron, and cobalt-containing raw material
PH12019501436A PH12019501436A1 (en) 2016-12-23 2019-06-21 Method for recovering nickel and cobalt from nickel, iron, and cobalt-containing raw material

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CN113293296A (zh) * 2021-05-31 2021-08-24 中伟新材料股份有限公司 一种氧化镍矿熔融还原硫化生产低冰镍的方法
CN113860392A (zh) * 2021-09-18 2021-12-31 江西江钨钴业有限公司 一种利用钴豆、钴板酸溶制备电池级硫酸钴、氯化钴的方法
CN113942986A (zh) * 2021-09-27 2022-01-18 荆门市格林美新材料有限公司 一种从镍铁合金中回收镍和铁的方法
CN114427037A (zh) * 2022-01-06 2022-05-03 中国恩菲工程技术有限公司 从低浓度镍钴溶液中连续化富集镍钴的方法
WO2023050806A1 (fr) * 2021-09-30 2023-04-06 广东邦普循环科技有限公司 Matériau d'électrode positive à base de phosphate ferrique de sodium dopé, son procédé de préparation et son application

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CN112779419A (zh) * 2020-12-24 2021-05-11 浙江华友钴业股份有限公司 一种镍钴锰铜溶液常压除铁铝硅的方法
CN113044821A (zh) * 2021-02-04 2021-06-29 湖南邦普循环科技有限公司 一种镍铁合金资源化回收的方法和应用
CN113293296A (zh) * 2021-05-31 2021-08-24 中伟新材料股份有限公司 一种氧化镍矿熔融还原硫化生产低冰镍的方法
CN113293296B (zh) * 2021-05-31 2024-04-26 中伟新材料股份有限公司 一种氧化镍矿熔融还原硫化生产低冰镍的方法
CN113860392A (zh) * 2021-09-18 2021-12-31 江西江钨钴业有限公司 一种利用钴豆、钴板酸溶制备电池级硫酸钴、氯化钴的方法
CN113942986A (zh) * 2021-09-27 2022-01-18 荆门市格林美新材料有限公司 一种从镍铁合金中回收镍和铁的方法
CN113942986B (zh) * 2021-09-27 2023-06-16 荆门市格林美新材料有限公司 一种从镍铁合金中回收镍和铁的方法
GB2618695A (en) * 2021-09-30 2023-11-15 Guangdong Brunp Recycling Technology Co Ltd Doped sodium ferric phosphate positive electrode material, preparation method therefor and application thereof
WO2023050806A1 (fr) * 2021-09-30 2023-04-06 广东邦普循环科技有限公司 Matériau d'électrode positive à base de phosphate ferrique de sodium dopé, son procédé de préparation et son application
CN114427037A (zh) * 2022-01-06 2022-05-03 中国恩菲工程技术有限公司 从低浓度镍钴溶液中连续化富集镍钴的方法
CN114427037B (zh) * 2022-01-06 2023-09-29 中国恩菲工程技术有限公司 从低浓度镍钴溶液中连续化富集镍钴的方法

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