WO2022213679A1 - Method for leaching nickel-ammonia solution from nickel-iron alloy in wet process and application - Google Patents

Method for leaching nickel-ammonia solution from nickel-iron alloy in wet process and application Download PDF

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WO2022213679A1
WO2022213679A1 PCT/CN2021/142555 CN2021142555W WO2022213679A1 WO 2022213679 A1 WO2022213679 A1 WO 2022213679A1 CN 2021142555 W CN2021142555 W CN 2021142555W WO 2022213679 A1 WO2022213679 A1 WO 2022213679A1
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nickel
iron
ammonia
leaching
solution
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PCT/CN2021/142555
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French (fr)
Chinese (zh)
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何芳
李长东
阮丁山
陈若葵
乔延超
邓浩臻
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Publication of WO2022213679A1 publication Critical patent/WO2022213679A1/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
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
    • 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
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the field of metallurgy, and in particular relates to a method and application of a nickel-iron alloy wet leaching nickel-ammonia solution.
  • Nickel is an important strategic metal and is widely used in key materials such as stainless steel, superalloys, fuel cells and high-tech
  • the current sources of nickel resources are mainly two kinds of nickel sulfide ore and nickel oxide ore (ie laterite nickel ore) in crustal resources, of which 30% are nickel sulfide ore and 70% are laterite nickel ore.
  • the production of nickel is in short supply, and the high-quality nickel sulfide ore is gradually being mined, which makes the mining and application of laterite nickel ore become more and more extensive.
  • Laterite nickel ore has become the main raw material for the production of ferronickel products.
  • the process principles of processing different ores can be summarized as: (1) fire process; (2) wet ammonia leaching process; (3) wet pressure acid leaching process.
  • the fire process requires a higher nickel grade, and for laterite nickel ore with a nickel content of about 1%, the wet ammonia leaching process can be used.
  • the problems of higher requirements, high consumption of auxiliary materials, serious scarring of the pressurizing valve, and high operating and production costs directly restrict the development of the enterprise.
  • the wet ammonia leaching process has weak corrosive materials, weak equipment material requirements, easy processing and production, and adopts atmospheric pressure leaching, the equipment structure is simple, and the reagents can be recycled.
  • the nickel metal recovery rate is generally about 80%. If nickel-iron alloy powder is used with conventional ammonium carbonate and ammonium bicarbonate systems, the leaching rate is generally about 90%. The purity of the obtained iron concentrate is less than 80%, and an additional ammonium source is required to leaching the iron ore.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
  • the present invention proposes a method and application of a nickel-iron alloy wet leaching of nickel-ammonia solution, the method can realize the separation of nickel and iron in nickel-iron, and the recovery rate of nickel is greater than 93.2%, and the recovery rate of iron is greater than 99.2%, Nickel is used directly for precursor synthesis and iron is sold directly as iron source.
  • the present invention adopts the following technical solutions:
  • a method for nickel-iron alloy wet leaching of nickel-ammonia solution comprising the following steps:
  • the crude nickel-iron alloy is obtained by reducing and roasting laterite nickel ore, and the content of nickel in the crude nickel-iron alloy is 15%-40%, and the content of iron is 60%-85%. %, the content of copper is 1-1.5%, the content of sulfur is 0.01-0.2%, and the content of cobalt is 0.5-0.8%.
  • the temperature of the oxidative roasting is 1200° C. ⁇ 1500° C.
  • the time of the oxidative roasting is 0.5 ⁇ 5 h.
  • the oxygen source of the oxidative roasting is oxygen or air. More preferably, the air is dehydrated air.
  • the particle size of the nickel-iron oxide powder is less than 60 mesh.
  • the lye solution is obtained by mixing ammonium salt and ammonia water; the ammonium salt is at least one of ammonium sulfate, ammonium hydrogen sulfate, and ammonium carbonate.
  • the dosage of NH 4 + is 1.0-3.0 times of the theoretical dosage.
  • the liquid-solid ratio of the alkali solution and the nickel-iron oxide powder is (2-4): 1 mL/g.
  • the stirring speed is 400r/min ⁇ 800r/min.
  • the heating temperature is 60°C to 90°C.
  • the time of the ammonia immersion reaction is 3-6 hours.
  • the pH of the slurry is also detected to be 10-12 before the filtration.
  • the iron slag is a mixture of magnetite and hematite.
  • step (2) a process of washing the iron slag is also included; the liquid-solid ratio of the solvent used in the washing and the iron slag is (2-4): 1 mL/g.
  • the number of times of the washing is 3 to 5 times.
  • the extractant used in the extraction is P507.
  • the degreasing substance used in the degreasing is activated carbon.
  • step (3) it also includes synthesizing the nickel-ammonia solution, that is, by evaporating ammonia to the solution, to obtain a ternary battery positive electrode material precursor and ammonium-containing wastewater.
  • the alkaline buffer solution is added to the ammonium-containing waste water to adjust the pH to be alkaline, and then the ammonia is evaporated by heating, and the ammonia water obtained after cooling is reused for ammonia leaching.
  • the alkaline buffer is at least one of sodium hydroxide, potassium hydroxide or sodium carbonate; the concentration of the alkaline buffer is 1-5 mol/L.
  • the pH adjustment to alkaline is to adjust the pH to 10-12.
  • the present invention also provides the application of the above method in preparing the positive electrode material of the ternary battery.
  • the present invention first oxidizes and roasts ferronickel, sprays granulation again, and impregnates ammonia at atmospheric pressure, thus reducing the energy consumption of high-pressure leaching, and the nickel-ammonia solution obtained simultaneously is directly used for the synthesis of ternary precursors, which reduces the amount of time in the synthesis process.
  • a source of ammonium needs to be introduced.
  • the nickel-ammonia solution obtained by the present invention is directly used for the synthesis of precursors, and the iron oxide with a purity of more than 93% can be directly sold as an iron source for iron and steel plants.
  • the invention has the advantages of short technological process, easy control of technical conditions and simple operation, and the nickel in the nickel-iron alloy can be made into the original solution for synthesizing the ternary precursor in one process.
  • FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
  • Crude nickel-iron alloy from a laterite nickel ore processing plant in Indonesia (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Under the condition of introducing oxygen, oxidative roasting is carried out, and the roasting temperature is 1300 ° C, and the roasted molten slurry is sprayed and granulated, and sieved to obtain nickel-iron oxide powder with a particle size of less than 100 mesh (>95%);
  • the iron slag was washed 3 times at a liquid-solid ratio of 2:1 ml/g to obtain iron ore.
  • the measured iron ore contained 0.15% nickel and 93.6% iron. It can be sold directly as a product, and the leaching rates of nickel and cobalt in this process are 98.2% and 94.1% respectively;
  • the leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5ppm, and then the raffinate is deoiled, and the oil in the liquid after deoiling is controlled to be less than 0.5ppm, that is, the nickel ammonia solution is directly used as a precursor.
  • Synthesis can obtain the precursor that meets the requirements, the synthetic wastewater is added with liquid caustic soda, the pH of the wastewater is adjusted to 11, and the ammonia is distilled, and the recovered ammonia water can be recycled.
  • Table 1 shows the content of each element in the iron concentrate of Example 1. From Table 1, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 93.6%, which can be directly sold as a product.
  • Table 2 is the concentration of each element in the nickel-ammonia solution of Example 1. It can be obtained from Table 2.
  • the leaching rate of nickel in the crude nickel-iron alloy is 98.2%, the leaching rate of cobalt is 94.1%, and the rest of the impurities are free.
  • the nickel ammonia solution can be used for the preparation of ternary precursors.
  • Fig. 1 is the process flow diagram of embodiment 1, as can be seen from the figure, through the process of high temperature oxidation-spray granulation-atmospheric leaching-extraction copper removal-synthesis precursor, the crude nickel-iron alloy is subjected to wet leaching to obtain The nickel-ammonia solution is directly used for precursor synthesis, and iron oxide is directly sold as an iron source for iron and steel plants.
  • Crude nickel-iron alloy from a laterite nickel ore processing plant in Indonesia (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Under the condition of introducing oxygen, oxidative roasting is carried out, and the roasting temperature is 1350 ° C, and the roasted molten slurry is sprayed and granulated, and sieved to obtain nickel-iron oxide powder with a particle size of less than 100 mesh (>95%);
  • the iron slag was washed 3 times at a liquid-solid ratio of 3:1 ml/g to obtain iron ore.
  • the measured iron ore contained 0.12% nickel and 94.2% iron. It can be sold directly as a product, and the leaching rates of nickel and cobalt in this process are 97.7% and 96.3% respectively;
  • the leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5 ppm, and then the raffinate is deoiled, and the oil in the liquid after degreasing is controlled to be less than 0.5 ppm, that is, the nickel ammonia solution is directly used as a precursor.
  • Synthesis can obtain the precursor that meets the requirements, the synthetic wastewater is added with sodium carbonate, the pH of the wastewater is adjusted to 11.5, and the ammonia is distilled, and the recovered ammonia water can be recycled.
  • Table 3 shows the content of each element in the iron concentrate of Example 2. From Table 3, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 94.2%, which can be directly sold as a product.
  • Table 4 shows the content of each element in the bottom liquid used for the synthesis of the ternary precursor in Example 2. It can be obtained from Table 4 that the leaching rate of nickel in the crude nickel-iron alloy is 95.4%, the leaching rate of cobalt is 96.3%, and the other The impurity removal rates of impurities are all greater than 99.9%, and the nickel sulfate hexahydrate of Example 2 can be used for the preparation of ternary precursors.
  • Crude nickel-iron alloy from a laterite nickel ore processing plant in Indonesia (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Under the condition of introducing oxygen, oxidative roasting is carried out, and the roasting temperature is 1350 ° C, and the roasted molten slurry is sprayed and granulated, and sieved to obtain nickel-iron oxide powder with a particle size of less than 100 mesh (>95%);
  • the iron slag was washed twice with a liquid-solid ratio of 4:1 ml/g.
  • the measured iron ore contained 0.12% nickel and 94.9% iron, which can be directly used as a product.
  • the leaching rates of nickel and cobalt in this process are 93.7% and 95.2% respectively;
  • the leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5ppm, and then the raffinate is deoiled, and the oil in the liquid after deoiling is controlled to be less than 0.5ppm, that is, the nickel ammonia solution is directly used as a precursor.
  • Synthesis can obtain a precursor that meets the requirements. After the synthesis, potassium hydroxide is added to the wastewater, the pH of the wastewater is adjusted to 12, and ammonia is distilled, and the recovered ammonia water can be recycled.
  • Table 5 shows the content of each element in the iron concentrate of Example 3. From Table 5, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 94.9%, which can be directly sold as a product.
  • Table 6 is the content of each element in the nickel-ammonia solution of Example 3. It can be obtained from Table 6.
  • the leaching rate of nickel in the crude nickel-iron alloy is 93.7%, the leaching rate of cobalt is 95.2%, and there are no other impurities.
  • the nickel-ammonia solution It can be used for the preparation of ternary precursors. Comparative Example 1 (Compared with Example 1, no oxidative granulation was performed)
  • the method for wet leaching nickel-ammonia solution of nickel-iron alloy of the present comparative example comprises the following steps:
  • Crude nickel-iron alloy from a laterite nickel ore processing plant in Indonesia (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Crushing and sieving to obtain nickel-iron alloy powder with particle size less than 100 mesh (>95%);
  • the leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5ppm, then the raffinate is deoiled, and the oil in the liquid after the degreasing is controlled to be less than 0.5ppm to obtain a nickel-ammonia solution, and the synthetic wastewater Add liquid caustic soda, adjust the pH of wastewater to 11, and steam ammonia, and the recovered ammonia water can be recycled.
  • Table 7 shows the content of each element in the iron ore of Comparative Example 1. It can be obtained from Table 5 that the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 92.2%.
  • Table 8 shows the content of each element in the nickel-ammonia solution of Comparative Example 1. From Table 8, the leaching rate of nickel in the crude nickel-iron alloy is 62.49%, which cannot be directly used for precursor synthesis.
  • the effect is poor, because there is no oxidative roasting, nickel and iron in the nickel-iron alloy are both simple substances, and iron and ammonia water will not react, but the obtained iron slag still contains high content of iron slag. Ni; at the same time, the reaction degree of nickel and ammonia water is also weak, and the leaching rate of nickel needs to be improved by pressurized oxidation leaching, so the leaching rate of nickel in the obtained nickel-ammonia solution is low.

Abstract

The present invention relates to the field of metallurgy. Disclosed are a method for leaching a nickel-ammonia solution from a nickel-iron alloy in a wet process and an application. The method comprises the following steps: performing oxidizing roasting on a crude nickel-iron alloy, and then performing spray granulation to obtain iron nickel oxide powder; adding the iron nickel oxide powder into an alkali solution, heating, performing ammonia leaching reaction, and filtering to obtain iron slag and a leachate; and extracting the leachate, and removing oil from a raffinate, thereby obtaining a nickel-ammonia solution. According to the present invention, nickel and iron are oxidized and roasted, and then spray granulation and atmospheric-pressure ammonia leaching are performed, such that high-pressure leaching energy consumption is saved; in addition, the obtained nickel-ammonia solution is directly used for ternary precursor synthesis, such that an ammonium source that should have been introduced in a synthesis process is saved.

Description

一种镍铁合金湿法浸出镍氨溶液的方法和应用A kind of method and application of nickel-iron alloy wet leaching nickel-ammonia solution 技术领域technical field
本发明属于冶金领域，具体涉及一种镍铁合金湿法浸出镍氨溶液的方法和应用。The invention belongs to the field of metallurgy, and in particular relates to a method and application of a nickel-iron alloy wet leaching nickel-ammonia solution.
背景技术Background technique
随着新能源行业的兴起，尤其是高镍电池的普及，镍的需求量正在逐渐增大，镍是一种重要的战略金属，广泛应用于不锈钢、高温合金、燃料电池等关键材料和高新技术领域，目前镍资源的来源主要是地壳资源中的硫化镍矿和氧化镍矿(即红土镍矿)两种，其中30％为硫化镍矿、70％为红土镍矿。且随着不锈钢产业的快速发展，使镍的生产供不应求，优质硫化镍矿逐渐开采殆尽，促使红土镍矿的开采应用变得越发广泛。With the rise of the new energy industry, especially the popularity of high-nickel batteries, the demand for nickel is gradually increasing. Nickel is an important strategic metal and is widely used in key materials such as stainless steel, superalloys, fuel cells and high-tech In the field, the current sources of nickel resources are mainly two kinds of nickel sulfide ore and nickel oxide ore (ie laterite nickel ore) in crustal resources, of which 30% are nickel sulfide ore and 70% are laterite nickel ore. And with the rapid development of the stainless steel industry, the production of nickel is in short supply, and the high-quality nickel sulfide ore is gradually being mined, which makes the mining and application of laterite nickel ore become more and more extensive.
红土镍矿已经成为生产镍铁产品的主要原料。处理不同矿石的工艺原则流程可归纳为：(1)火法流程；(2)湿法氨浸流程；(3)湿法加压酸浸流程。火法流程要求较高的镍品位，而对于镍含量在1％左右的红土镍矿则可采用湿法氨浸流程，如用湿法加压酸浸流程，生产工艺复杂、工艺环节、对设备的要求较高、辅料消耗高、加压阀结疤严重、运营生产成本高等问题，直接制约着企业的发展。而选择湿法氨浸流程物料腐蚀性弱，设备材质要求较弱，易于加工制作，并采用常压浸出，设备结构简单，试剂可循环使用。Laterite nickel ore has become the main raw material for the production of ferronickel products. The process principles of processing different ores can be summarized as: (1) fire process; (2) wet ammonia leaching process; (3) wet pressure acid leaching process. The fire process requires a higher nickel grade, and for laterite nickel ore with a nickel content of about 1%, the wet ammonia leaching process can be used. The problems of higher requirements, high consumption of auxiliary materials, serious scarring of the pressurizing valve, and high operating and production costs directly restrict the development of the enterprise. However, the wet ammonia leaching process has weak corrosive materials, weak equipment material requirements, easy processing and production, and adopts atmospheric pressure leaching, the equipment structure is simple, and the reagents can be recycled.
目前的氨浸出过程中，若直接用红土矿作为原料镍金属回收率一般在80％左右，若用镍铁合金粉配以常规的碳酸铵、碳酸氢铵体系，浸出率一般在90％左右，但得到铁精矿纯度不到80％，而且还需要外加铵源进行浸出铁矿。In the current ammonia leaching process, if laterite ore is used directly as raw material, the nickel metal recovery rate is generally about 80%. If nickel-iron alloy powder is used with conventional ammonium carbonate and ammonium bicarbonate systems, the leaching rate is generally about 90%. The purity of the obtained iron concentrate is less than 80%, and an additional ammonium source is required to leaching the iron ore.
发明内容SUMMARY OF THE INVENTION
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种镍铁合金湿法浸出镍氨溶液的方法和应用，该方法能实现镍铁中的镍和铁分离，且镍回收率大于93.2％，铁的回收率大于99.2％，镍直接用于前驱体合成，铁作为铁源直接销售。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method and application of a nickel-iron alloy wet leaching of nickel-ammonia solution, the method can realize the separation of nickel and iron in nickel-iron, and the recovery rate of nickel is greater than 93.2%, and the recovery rate of iron is greater than 99.2%, Nickel is used directly for precursor synthesis and iron is sold directly as iron source.
为实现上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种镍铁合金湿法浸出镍氨溶液的方法，包括以下步骤：A method for nickel-iron alloy wet leaching of nickel-ammonia solution, comprising the following steps:
(1)将粗制镍铁合金氧化焙烧，再进行喷雾造粒，得到氧化镍铁粉；(1) oxidative roasting of crude nickel-iron alloy is carried out, and then spray granulation is carried out to obtain nickel-iron oxide powder;
(2)将所述氧化镍铁粉加入碱溶液中，加热，进行氨浸反应，过滤，得到铁渣和浸出液；(2) adding described nickel oxide iron powder to alkaline solution, heating, carrying out ammonia leaching reaction, filtering to obtain iron slag and leachate;
(3)将所述浸出液进行萃取，取萃余液进行除油，即得所述镍氨溶液。(3) extracting the leaching solution, extracting the raffinate for degreasing, to obtain the nickel ammonia solution.
优选地，步骤(1)中，所述粗制镍铁合金是将红土镍矿经还原焙烧所得，所述粗制镍铁合金中镍的含量为15％-40％，铁的含量为60％-85％，铜的含量为1-1.5％，硫的含量为0.01-0.2％，钴的含量为0.5-0.8％。Preferably, in step (1), the crude nickel-iron alloy is obtained by reducing and roasting laterite nickel ore, and the content of nickel in the crude nickel-iron alloy is 15%-40%, and the content of iron is 60%-85%. %, the content of copper is 1-1.5%, the content of sulfur is 0.01-0.2%, and the content of cobalt is 0.5-0.8%.
优选地，步骤(1)中，所述氧化焙烧的温度为1200℃～1500℃，氧化焙烧的时间为0.5～5h。Preferably, in step (1), the temperature of the oxidative roasting is 1200° C.˜1500° C., and the time of the oxidative roasting is 0.5˜5 h.
优选地，步骤(1)中，所述氧化焙烧的氧源为氧气或空气。更优选地，所述空气为经过脱水后的空气。Preferably, in step (1), the oxygen source of the oxidative roasting is oxygen or air. More preferably, the air is dehydrated air.
优选地，步骤(1)中，所述氧化镍铁粉的粒径＜60目。Preferably, in step (1), the particle size of the nickel-iron oxide powder is less than 60 mesh.
优选地，步骤(2)中，所述碱液是由铵盐和氨水混合得到；所述铵盐为硫酸铵、硫酸氢铵、碳酸铵中的至少一种。Preferably, in step (2), the lye solution is obtained by mixing ammonium salt and ammonia water; the ammonium salt is at least one of ammonium sulfate, ammonium hydrogen sulfate, and ammonium carbonate.
更优选地，所述NH 4 +用量为理论用量的1.0～3.0倍。 More preferably, the dosage of NH 4 + is 1.0-3.0 times of the theoretical dosage.
优选地，步骤(2)中，所述碱液和氧化镍铁粉的液固比为(2-4)：1mL/g。Preferably, in step (2), the liquid-solid ratio of the alkali solution and the nickel-iron oxide powder is (2-4): 1 mL/g.
优选地，步骤(2)中，所述搅拌的速度为400r/min～800r/min。Preferably, in step (2), the stirring speed is 400r/min～800r/min.
优选地，步骤(2)中，所述加热的温度为60℃～90℃。Preferably, in step (2), the heating temperature is 60°C to 90°C.
优选地，步骤(2)中，所述氨浸反应的时间为3～6h。Preferably, in step (2), the time of the ammonia immersion reaction is 3-6 hours.
优选地，步骤(2)中，所述过滤前还要检测浆体的pH为10-12。Preferably, in step (2), the pH of the slurry is also detected to be 10-12 before the filtration.
优选地，步骤(2)中，所述铁渣为磁铁矿和赤铁矿的混合物。Preferably, in step (2), the iron slag is a mixture of magnetite and hematite.
优选地，步骤(2)中，还包括对所述铁渣进行洗涤的过程；所述洗涤中使用的溶剂和铁渣的的液固比为(2-4)：1mL/g。Preferably, in step (2), a process of washing the iron slag is also included; the liquid-solid ratio of the solvent used in the washing and the iron slag is (2-4): 1 mL/g.
更优选地，所述洗涤的次数为3～5次。More preferably, the number of times of the washing is 3 to 5 times.
优选地，步骤(3)中，所述萃取使用的萃取剂为P507。Preferably, in step (3), the extractant used in the extraction is P507.
优选地，步骤(3)中，所述除油采用的除油物为活性碳。Preferably, in step (3), the degreasing substance used in the degreasing is activated carbon.
优选地，步骤(3)中，还包括将镍氨溶液进行合成，即通过对溶液进行蒸氨，得 到三元电池正极材料前驱体和含铵废水。Preferably, in step (3), it also includes synthesizing the nickel-ammonia solution, that is, by evaporating ammonia to the solution, to obtain a ternary battery positive electrode material precursor and ammonium-containing wastewater.
更优选地，将碱性缓冲液加入所述含铵废水中调pH至碱性，再进行加热蒸氨，冷却后得到的氨水重新用于氨浸。More preferably, the alkaline buffer solution is added to the ammonium-containing waste water to adjust the pH to be alkaline, and then the ammonia is evaporated by heating, and the ammonia water obtained after cooling is reused for ammonia leaching.
更优选地，所述碱性缓冲液为氢氧化钠、氢氧化钾或碳酸钠中的至少一种；所述碱性缓冲液的浓度为1～5mol/L。More preferably, the alkaline buffer is at least one of sodium hydroxide, potassium hydroxide or sodium carbonate; the concentration of the alkaline buffer is 1-5 mol/L.
更优选地，所述调pH至碱性是将pH调至10-12。More preferably, the pH adjustment to alkaline is to adjust the pH to 10-12.
本发明的反应原理：Reaction principle of the present invention:
2NiO+8NH 3+2(NH 4) 2SO 4→2[Ni(NH 3) 6]SO 4+2H 2O； 2NiO+8NH 3 +2(NH 4 ) 2 SO 4 →2[Ni(NH 3 ) 6 ]SO 4 +2H 2 O;
2CoO+8NH 3+2(NH 4) 2SO 4→2[Ni(NH 3) 6]SO 4+2H 2O； 2CoO+8NH 3 +2(NH 4 ) 2 SO 4 →2[Ni(NH 3 ) 6 ]SO 4 +2H 2 O;
2CuO+8NH 3+2(NH 4) 2SO 4→2[Cu(NH 3) 6]SO 4+2H 2O。 2CuO +8NH3+ 2 ( NH4 ) 2SO4 →2[Cu( NH3 ) 6 ] SO4 + 2H2O.
本发明还提供上述的方法在制备三元电池正极材料中的应用。The present invention also provides the application of the above method in preparing the positive electrode material of the ternary battery.
相对于现有技术，本发明的有益效果如下：With respect to the prior art, the beneficial effects of the present invention are as follows:
1.本发明先将镍铁氧化焙烧，再喷雾造粒，常压氨浸，这样就减少了高压浸出能耗，同时得到的镍氨溶液直接用于三元前驱体合成，减少了合成过程中需要引入的铵源。1. the present invention first oxidizes and roasts ferronickel, sprays granulation again, and impregnates ammonia at atmospheric pressure, thus reducing the energy consumption of high-pressure leaching, and the nickel-ammonia solution obtained simultaneously is directly used for the synthesis of ternary precursors, which reduces the amount of time in the synthesis process. A source of ammonium needs to be introduced.
2.本发明得到的镍氨溶液直接用于前驱体合成，纯度大于93％的氧化铁可直接销售，作为钢铁厂铁源。本发明工艺流程短，技术条件易控，操作简单，一道工序便将镍铁合金中的镍制成了三元前驱体合成的原液。2. The nickel-ammonia solution obtained by the present invention is directly used for the synthesis of precursors, and the iron oxide with a purity of more than 93% can be directly sold as an iron source for iron and steel plants. The invention has the advantages of short technological process, easy control of technical conditions and simple operation, and the nickel in the nickel-iron alloy can be made into the original solution for synthesizing the ternary precursor in one process.
附图说明Description of drawings
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, wherein:
图1为本发明的实施例1的工艺流程图。FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of The scope of protection of the present invention.
实施例1Example 1
本实施例的镍铁合金湿法浸出镍氨溶液的方法，包括以下步骤：The method for nickel-iron alloy wet leaching of nickel-ammonia solution of the present embodiment comprises the following steps:
(1)粗制镍铁合金(取自印尼某红土镍矿加工厂产品)(粗制镍铁合金中的成分为： Fe 70％，Ni 28％，Cu 0.5％，S 0.1％，Co 0.6％)100g在通入氧气的条件下，氧化焙烧，焙烧温度为1300℃，焙烧的熔融浆体进行喷雾造粒，过筛，得到粒径小于100目(＞95％)的氧化镍铁粉；(1) Crude nickel-iron alloy (from a laterite nickel ore processing plant in Indonesia) (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Under the condition of introducing oxygen, oxidative roasting is carried out, and the roasting temperature is 1300 ° C, and the roasted molten slurry is sprayed and granulated, and sieved to obtain nickel-iron oxide powder with a particle size of less than 100 mesh (>95%);
(2)在密闭的容器中，按照氧化镍铁粉中镍钴铜所需耗铵理论量的1.5倍、按液固比为2：1加入氨水和硫酸铵的混合溶液，放入70℃的水浴锅中，以转速400r/min恒温加入，溢流出的氨气通过气流泵，再泵入反应的浆体中，实现氨的循环利用，反应总时间控制在4h，反应结束后检测浆料pH＝10.0，并趁热过滤，得到铁渣和浸出液，铁渣按液固比为2：1ml/g洗涤3次后，得到铁矿，测的铁矿中含镍0.15％，含铁93.6％，可作为产品直接出售，此过程镍钴的浸出率分别为98.2％、94.1％；(2) In a closed container, add a mixed solution of ammonia water and ammonium sulfate according to 1.5 times the theoretical amount of ammonium consumption required for nickel, cobalt and copper in the nickel-iron oxide powder, and at a liquid-solid ratio of 2:1, and put it into a 70° C. In the water bath, it was added at a constant temperature of 400 r/min, and the overflowed ammonia gas was pumped through the airflow pump and then pumped into the reacted slurry to realize the recycling of ammonia. The total reaction time was controlled at 4h, and the pH of the slurry was detected after the reaction. = 10.0, and filtered while hot to obtain iron slag and leaching solution. The iron slag was washed 3 times at a liquid-solid ratio of 2:1 ml/g to obtain iron ore. The measured iron ore contained 0.15% nickel and 93.6% iron. It can be sold directly as a product, and the leaching rates of nickel and cobalt in this process are 98.2% and 94.1% respectively;
(3)将浸出液经过萃取除铜，控制萃余液中铜浓度＜5ppm，再将萃余液除油，控制除油后液中的油＜0.5ppm，即得镍氨溶液直接用于前驱体合成，能够得到符合要求的前驱体，合成后的废水加入液碱，调节废水的pH至11，并蒸氨，回收的氨水可以循环使用。(3) The leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5ppm, and then the raffinate is deoiled, and the oil in the liquid after deoiling is controlled to be less than 0.5ppm, that is, the nickel ammonia solution is directly used as a precursor. Synthesis, can obtain the precursor that meets the requirements, the synthetic wastewater is added with liquid caustic soda, the pH of the wastewater is adjusted to 11, and the ammonia is distilled, and the recovered ammonia water can be recycled.
表1：实施例1的铁矿中各元素含量Table 1: Content of each element in the iron ore of Example 1
   FeFe NiNi CoCo SS CuCu
含量/％content/% 93.693.6 0.150.15 0.090.09 0.010.01 0.050.05
回收率/％Recovery rate/% 99.9999.99 \\ \\ \\ \\
表1为实施例1的铁精矿中各元素含量，从表1可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为93.6％，可作为产品直接出售。Table 1 shows the content of each element in the iron concentrate of Example 1. From Table 1, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 93.6%, which can be directly sold as a product.
表2：镍氨溶液中各元素浓度Table 2: Concentrations of Elements in Nickel-Ammonia Solution
   NiNi FeFe CoCo CuCu
浓度g/LConcentrationg/L 137.48137.48 0.0010.001 2.822.82 0.0030.003
浸出率/％Leach rate/% 98.298.2 00 94.194.1 00
表2为实施例1的镍氨溶液中各元素浓度，从表2可得，粗制镍铁合金中镍的浸出率为98.2％，钴的浸出率为94.1％，其余杂质均无，实施例2的镍氨溶液可用于三元前驱体的制备。Table 2 is the concentration of each element in the nickel-ammonia solution of Example 1. It can be obtained from Table 2. The leaching rate of nickel in the crude nickel-iron alloy is 98.2%, the leaching rate of cobalt is 94.1%, and the rest of the impurities are free. Example 2 The nickel ammonia solution can be used for the preparation of ternary precursors.
图1为实施例1的工艺流程图，从图中可得，经过通过高温氧化-喷雾造粒-常压浸出-萃取除铜-合成前驱体的工艺将粗制镍铁合金经过湿法浸出，得到的镍氨溶液直接用 于前驱体合成，氧化铁直接销售，作为钢铁厂铁源。Fig. 1 is the process flow diagram of embodiment 1, as can be seen from the figure, through the process of high temperature oxidation-spray granulation-atmospheric leaching-extraction copper removal-synthesis precursor, the crude nickel-iron alloy is subjected to wet leaching to obtain The nickel-ammonia solution is directly used for precursor synthesis, and iron oxide is directly sold as an iron source for iron and steel plants.
实施例2Example 2
本实施例的镍铁合金湿法浸出镍氨溶液的方法，包括以下步骤：The method for nickel-iron alloy wet leaching of nickel-ammonia solution of the present embodiment comprises the following steps:
(1)粗制镍铁合金(取自印尼某红土镍矿加工厂产品)(粗制镍铁合金中的成分为：Fe 70％，Ni 28％，Cu 0.5％，S 0.1％，Co 0.6％)100g在通入氧气的条件下，氧化焙烧，焙烧温度为1350℃，焙烧的熔融浆体进行喷雾造粒，过筛，得到粒径小于100目(＞95％)的氧化镍铁粉；(1) Crude nickel-iron alloy (from a laterite nickel ore processing plant in Indonesia) (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Under the condition of introducing oxygen, oxidative roasting is carried out, and the roasting temperature is 1350 ° C, and the roasted molten slurry is sprayed and granulated, and sieved to obtain nickel-iron oxide powder with a particle size of less than 100 mesh (>95%);
(2)在密闭的容器中，按照氧化镍铁粉中镍钴铜所需耗铵理论量的2.0倍、按液固比为3：1加入氨水和硫酸铵的混合溶液，放入80℃的水浴锅中，以转速600r/min恒温加入，溢流出的氨气通过气流泵，再泵入反应的浆体中，实现氨的循环利用，反应总时间控制在5h，反应结束后检测浆料pH＝10.5，并趁热过滤，得到铁渣和浸出液，铁渣按液固比为3：1ml/g洗涤3次后，得到铁矿，测的铁矿中含镍0.12％，含铁94.2％，可作为产品直接出售，此过程镍钴的浸出率分别为97.7％、96.3％；(2) In a closed container, add a mixed solution of ammonia water and ammonium sulfate according to 2.0 times the theoretical amount of ammonium consumption required by nickel-cobalt-copper in the nickel-iron oxide powder, and at a liquid-solid ratio of 3:1, and put it into a 80° C. In the water bath, the constant temperature was added at a rotating speed of 600r/min, and the overflowed ammonia gas was pumped through the airflow pump and then pumped into the reacted slurry to realize the recycling of ammonia. The total reaction time was controlled at 5h, and the pH of the slurry was detected after the reaction. = 10.5, and filtered while hot to obtain iron slag and leachate. The iron slag was washed 3 times at a liquid-solid ratio of 3:1 ml/g to obtain iron ore. The measured iron ore contained 0.12% nickel and 94.2% iron. It can be sold directly as a product, and the leaching rates of nickel and cobalt in this process are 97.7% and 96.3% respectively;
(3)将浸出液经过萃取除铜，控制萃余液中铜浓度＜5ppm，再将萃余液除油，控制除油后液中的油＜0.5ppm，即得镍氨溶液直接用于前驱体合成，能够得到符合要求的前驱体，合成后的废水加入碳酸钠，调节废水的pH至11.5，并蒸氨，回收的氨水可以循环使用。(3) The leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5 ppm, and then the raffinate is deoiled, and the oil in the liquid after degreasing is controlled to be less than 0.5 ppm, that is, the nickel ammonia solution is directly used as a precursor. Synthesis, can obtain the precursor that meets the requirements, the synthetic wastewater is added with sodium carbonate, the pH of the wastewater is adjusted to 11.5, and the ammonia is distilled, and the recovered ammonia water can be recycled.
表3：铁渣中各元素含量Table 3: Content of each element in iron slag
   FeFe NiNi CoCo SS CuCu
含量/％content/% 94.294.2 0.120.12 0.050.05 0.020.02 0.030.03
回收率/％Recovery rate/% 99.9999.99 \\ \\ \\ \\
表3为实施例2的铁精矿中各元素含量，从表3可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为94.2％，可作为产品直接出售。Table 3 shows the content of each element in the iron concentrate of Example 2. From Table 3, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 94.2%, which can be directly sold as a product.
表4：镍氨溶液中各元素含量Table 4: Content of each element in nickel-ammonia solution
   NiNi FeFe CoCo CuCu
浓度g/LConcentrationg/L 89.0489.04 0.0010.001 1.931.93 0.0020.002
浸出率/％Leach rate/% 95.495.4 00 96.396.3 00
表4为实施例2的用于三元前驱体合成的底液中各元素含量，从表4可得，粗制镍 铁合金中镍的浸出率为95.4％，钴的浸出率为96.3％，其它杂质的除杂率均大于99.9％，实施例2的六水硫酸镍可用于三元前驱体的制备。Table 4 shows the content of each element in the bottom liquid used for the synthesis of the ternary precursor in Example 2. It can be obtained from Table 4 that the leaching rate of nickel in the crude nickel-iron alloy is 95.4%, the leaching rate of cobalt is 96.3%, and the other The impurity removal rates of impurities are all greater than 99.9%, and the nickel sulfate hexahydrate of Example 2 can be used for the preparation of ternary precursors.
实施例3Example 3
本实施例的镍铁合金湿法浸出镍氨溶液的方法，包括以下步骤：The method for nickel-iron alloy wet leaching of nickel-ammonia solution of the present embodiment comprises the following steps:
(1)粗制镍铁合金(取自印尼某红土镍矿加工厂产品)(粗制镍铁合金中的成分为：Fe 70％，Ni 28％，Cu 0.5％，S 0.1％，Co 0.6％)100g在通入氧气的条件下，氧化焙烧，焙烧温度为1350℃，焙烧的熔融浆体进行喷雾造粒，过筛，得到粒径小于100目(＞95％)的氧化镍铁粉；(1) Crude nickel-iron alloy (from a laterite nickel ore processing plant in Indonesia) (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Under the condition of introducing oxygen, oxidative roasting is carried out, and the roasting temperature is 1350 ° C, and the roasted molten slurry is sprayed and granulated, and sieved to obtain nickel-iron oxide powder with a particle size of less than 100 mesh (>95%);
(2)在密闭的容器中，按照氧化镍铁粉中镍钴铜所需耗铵理论量的2.0倍、按液固比为4：1加入氨水和硫酸铵的混合溶液，放入60℃的水浴锅中，以转速700r/min恒温加入，溢流出的氨气通过气流泵，再泵入反应的浆体中，实现氨的循环利用，反应总时间控制在6h，反应结束后检测浆料pH＝11.5，并趁热过滤，得到铁渣和浸出液，铁渣按液固比为4：1ml/g洗涤2次后，测的铁矿中含镍0.12％，含铁94.9％，可作为产品直接出售，此过程镍钴的浸出率分别为93.7％、95.2％；(2) In a closed container, add a mixed solution of ammonia water and ammonium sulfate according to 2.0 times the theoretical amount of ammonium consumption required by nickel-cobalt-copper in the nickel-iron oxide powder, according to the liquid-solid ratio of 4:1, and put it into a 60° C. In the water bath, it was added at a constant temperature of 700 r/min, and the overflowed ammonia gas was pumped through the airflow pump and then pumped into the reacted slurry to realize the recycling of ammonia. The total reaction time was controlled at 6h, and the pH of the slurry was detected after the reaction. = 11.5, and filtered while hot to obtain iron slag and leachate. The iron slag was washed twice with a liquid-solid ratio of 4:1 ml/g. The measured iron ore contained 0.12% nickel and 94.9% iron, which can be directly used as a product. For sale, the leaching rates of nickel and cobalt in this process are 93.7% and 95.2% respectively;
(3)将浸出液经过萃取除铜，控制萃余液中铜浓度＜5ppm，再将萃余液除油，控制除油后液中的油＜0.5ppm，即得镍氨溶液直接用于前驱体合成，能够得到符合要求的前驱体，合成后的废水加入氢氧化钾，调节废水的pH至12，并蒸氨，回收的氨水可以循环使用。(3) The leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5ppm, and then the raffinate is deoiled, and the oil in the liquid after deoiling is controlled to be less than 0.5ppm, that is, the nickel ammonia solution is directly used as a precursor. Synthesis can obtain a precursor that meets the requirements. After the synthesis, potassium hydroxide is added to the wastewater, the pH of the wastewater is adjusted to 12, and ammonia is distilled, and the recovered ammonia water can be recycled.
表5：铁渣中各元素含量Table 5: Content of each element in iron slag
   FeFe NiNi CoCo SS CuCu
含量/％content/% 94.994.9 0.110.11 0.060.06 0.020.02 0.010.01
回收率/％Recovery rate/% 99.9999.99 \\ \\ \\ \\
表5为实施例3的铁精矿中各元素含量，从表5可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为94.9％，可作为产品直接出售。Table 5 shows the content of each element in the iron concentrate of Example 3. From Table 5, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 94.9%, which can be directly sold as a product.
表6：镍氨溶液中各元素含量Table 6: Content of each element in nickel-ammonia solution
   NiNi FeFe CoCo CuCu
浓度/g/LConcentration/g/L 65.5965.59 0.0020.002 1.431.43 0.0030.003
浸出率/％Leach rate/% 93.793.7 00 95.295.2 00
表6为实施例3的镍氨溶液中各元素含量，从表6可得，粗制镍铁合金中镍的浸出率为93.7％，钴的浸出率为95.2％，其它杂质均无，镍氨溶液可用于三元前驱体的制备。对比例1(与实施例1相比，不进行氧化造粒)Table 6 is the content of each element in the nickel-ammonia solution of Example 3. It can be obtained from Table 6. The leaching rate of nickel in the crude nickel-iron alloy is 93.7%, the leaching rate of cobalt is 95.2%, and there are no other impurities. The nickel-ammonia solution It can be used for the preparation of ternary precursors. Comparative Example 1 (Compared with Example 1, no oxidative granulation was performed)
本对比例的镍铁合金湿法浸出镍氨溶液的方法，包括以下步骤：The method for wet leaching nickel-ammonia solution of nickel-iron alloy of the present comparative example comprises the following steps:
(1)粗制镍铁合金(取自印尼某红土镍矿加工厂产品)(粗制镍铁合金中的成分为：Fe 70％，Ni 28％，Cu 0.5％，S 0.1％，Co 0.6％)100g破碎，过筛，得到粒径小于100目(＞95％)的镍铁合金粉；(1) Crude nickel-iron alloy (from a laterite nickel ore processing plant in Indonesia) (the composition of the crude nickel-iron alloy is: Fe 70%, Ni 28%, Cu 0.5%, S 0.1%, Co 0.6%) 100g Crushing and sieving to obtain nickel-iron alloy powder with particle size less than 100 mesh (>95%);
(2)在密闭的容器中，按照镍铁合金粉中镍钴铜所需耗铵理论量的1.5倍、按液固比为2：1加入氨水和硫酸铵的混合溶液，放入70℃的水浴锅中，以转速400r/min恒温加入，溢流出的氨气通过气流泵，再泵入反应的浆体中，实现氨的循环利用，反应总时间控制在4h，反应结束后检测浆料pH＝10.0，并趁热过滤，得到铁渣和浸出液，铁渣按液固比为2：1ml/g洗涤3次后，得到铁矿；(2) In a closed container, add a mixed solution of ammonia water and ammonium sulfate according to 1.5 times the theoretical amount of ammonium consumption required for nickel-cobalt-copper in the nickel-iron alloy powder, and the liquid-solid ratio is 2:1, and put it into a water bath at 70 ° C. In the pot, it was added at a constant temperature of 400r/min, and the overflowed ammonia gas was pumped into the reacted slurry through the airflow pump to realize the recycling of ammonia. The total reaction time was controlled at 4h, and the pH of the slurry was detected after the reaction. 10.0, and filtered while hot to obtain iron slag and leachate, and the iron slag was washed 3 times at a liquid-solid ratio of 2:1 ml/g to obtain iron ore;
(3)将浸出液经过萃取除铜，控制萃余液中铜浓度＜5ppm，再将萃余液除油，控制除油后液中的油＜0.5ppm，即得镍氨溶液，合成后的废水加入液碱，调节废水的pH至11，并蒸氨，回收的氨水可以循环使用。(3) the leaching solution is extracted to remove copper, and the copper concentration in the raffinate is controlled to be less than 5ppm, then the raffinate is deoiled, and the oil in the liquid after the degreasing is controlled to be less than 0.5ppm to obtain a nickel-ammonia solution, and the synthetic wastewater Add liquid caustic soda, adjust the pH of wastewater to 11, and steam ammonia, and the recovered ammonia water can be recycled.
表7：对比例1的铁矿中各元素含量Table 7: Content of each element in the iron ore of Comparative Example 1
   FeFe NiNi CoCo SS CuCu
含量/％content/% 92.292.2 5.65.6 0.340.34 0.020.02 0.210.21
回收率/％Recovery rate/% 99.9999.99 \\ \\ \\ \\
表7为对比例1的铁矿中各元素含量，从表5可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为92.2％。Table 7 shows the content of each element in the iron ore of Comparative Example 1. It can be obtained from Table 5 that the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 92.2%.
表8：对比例1的镍氨溶液中各元素含量Table 8: Content of each element in the nickel-ammonia solution of Comparative Example 1
   NiNi CoCo SS FeFe CuCu
浓度/g/LConcentration/g/L 87.4887.48 0.980.98 0.530.53 0.0010.001 0.0020.002
浸出率/％Leach rate/% 62.4962.49 32.732.7 \\ 00 00
表8为对比例1的镍氨溶液中各元素含量，从表8可得，粗制镍铁合金中镍的浸出率为62.49％，不能直接用于前驱体合成。Table 8 shows the content of each element in the nickel-ammonia solution of Comparative Example 1. From Table 8, the leaching rate of nickel in the crude nickel-iron alloy is 62.49%, which cannot be directly used for precursor synthesis.
由对比例1的数据来看，效果较差，因为没有经过氧化焙烧，镍铁合金中的镍与铁 均为单质，铁与氨水不会发生反应，但得到的铁渣中仍含有含量较高的Ni；同时，镍与氨水的反应程度也较弱，需要进行加压氧化浸出才能提高其浸出率，因此得到的镍氨溶液中镍的浸出率较低。According to the data of Comparative Example 1, the effect is poor, because there is no oxidative roasting, nickel and iron in the nickel-iron alloy are both simple substances, and iron and ammonia water will not react, but the obtained iron slag still contains high content of iron slag. Ni; at the same time, the reaction degree of nickel and ammonia water is also weak, and the leaching rate of nickel needs to be improved by pressurized oxidation leaching, so the leaching rate of nickel in the obtained nickel-ammonia solution is low.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge possessed by those of ordinary skill in the art, various Variety. Furthermore, the embodiments of the present invention and features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种镍铁合金湿法浸出镍氨溶液的方法，其特征在于，包括以下步骤：A method for nickel-iron alloy wet leaching of nickel-ammonia solution, comprising the following steps:
    (1)将粗制镍铁合金进行氧化焙烧，再进行喷雾造粒，得到氧化镍铁粉；(1) oxidative roasting is carried out with crude nickel-iron alloy, and then spray granulation is carried out to obtain nickel-iron oxide powder;
    (2)将所述氧化镍铁粉加入碱溶液中，加热，进行氨浸反应，过滤，得到铁渣和浸出液；(2) adding described nickel oxide iron powder to alkaline solution, heating, carrying out ammonia leaching reaction, filtering to obtain iron slag and leachate;
    (3)将所述浸出液进行萃取，取萃余液进行除油，即得所述镍氨溶液。(3) extracting the leaching solution, extracting the raffinate for degreasing, to obtain the nickel ammonia solution.
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述粗制镍铁合金是将红土镍矿经还原焙烧所得，所述粗制镍铁合金中镍的含量为15％-40％，铁的含量为60％-85％，铜的含量为1-1.5％，硫的含量为0.01-0.2％，钴的含量为0.5-0.8％。The method according to claim 1, wherein in step (1), the crude nickel-iron alloy is obtained by reducing laterite nickel ore, and the content of nickel in the crude nickel-iron alloy is 15%-40%. %, the content of iron is 60%-85%, the content of copper is 1-1.5%, the content of sulfur is 0.01-0.2%, and the content of cobalt is 0.5-0.8%.
  3. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述氧化焙烧的温度为1200℃～1500℃，氧化焙烧的时间为0.5～5h。The method according to claim 1, wherein in step (1), the temperature of the oxidative roasting is 1200°C to 1500°C, and the time of the oxidative roasting is 0.5 to 5 h.
  4. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述氧化焙烧的氧源为氧气或空气。The method according to claim 1, wherein in step (1), the oxygen source of the oxidative roasting is oxygen or air.
  5. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述碱液是由铵盐和氨水混合得到；所述铵盐为硫酸铵、硫酸氢铵或碳酸铵中的至少一种。The method according to claim 1, wherein, in step (2), the lye is obtained by mixing ammonium salt and ammonia water; the ammonium salt is at least one of ammonium sulfate, ammonium hydrogen sulfate or ammonium carbonate kind.
  6. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述加热的温度为60℃～90℃；步骤(2)中，所述氨浸反应的时间为3～6h；步骤(2)中，所述过滤前还要检测浆体的pH为10-12。The method according to claim 1, characterized in that, in step (2), the heating temperature is 60°C to 90°C; in step (2), the time of the ammonia immersion reaction is 3 to 6h; step In (2), the pH of the slurry is also detected to be 10-12 before the filtration.
  7. 根据权利要求1所述的方法，其特征在于，步骤(2)中，还包括对所述铁渣进行洗涤的过程；所述洗涤中使用的溶剂和铁渣的的液固比为(2-4)：1mL/g。The method according to claim 1, characterized in that, in step (2), further comprising a process of washing the iron slag; the liquid-solid ratio of the solvent used in the washing and the iron slag is (2- 4): 1 mL/g.
  8. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述萃取使用的萃取剂为P507；步骤(3)中，所述除油采用的除油物为活性碳。The method according to claim 1, wherein in step (3), the extractant used in the extraction is P507; in step (3), the degreasing substance used in the degreasing is activated carbon.
  9. 根据权利要求1所述的方法，其特征在于，步骤(3)中，还包括将镍氨溶液进行合成，即通过对溶液进行蒸氨，得到三元电池正极材料前驱体和含铵废水。The method according to claim 1, characterized in that, in step (3), it further comprises synthesizing a nickel-ammonia solution, that is, by evaporating ammonia from the solution, to obtain a ternary battery positive electrode material precursor and ammonium-containing wastewater.
  10. 权利要求1-9任一项所述的方法在制备三元电池正极材料中的应用。Application of the method according to any one of claims 1 to 9 in preparing a positive electrode material for a ternary battery.
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