WO2023005406A1 - 一种利用低镍锍直接制备硫酸镍的方法、硫酸镍及其应用 - Google Patents

一种利用低镍锍直接制备硫酸镍的方法、硫酸镍及其应用 Download PDF

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WO2023005406A1
WO2023005406A1 PCT/CN2022/096308 CN2022096308W WO2023005406A1 WO 2023005406 A1 WO2023005406 A1 WO 2023005406A1 CN 2022096308 W CN2022096308 W CN 2022096308W WO 2023005406 A1 WO2023005406 A1 WO 2023005406A1
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nickel
solution
sulfate
supersaturated
matte
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English (en)
French (fr)
Inventor
余海军
钟应声
谢英豪
李爱霞
张学梅
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Priority to US18/282,133 priority Critical patent/US12199283B2/en
Priority to DE112022001037.1T priority patent/DE112022001037T5/de
Priority to MA62706A priority patent/MA62706A1/fr
Priority to ES202390159A priority patent/ES2957083R1/es
Publication of WO2023005406A1 publication Critical patent/WO2023005406A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • 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
    • C22B23/043—Sulfurated 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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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 technical field of hydrometallurgy, in particular to a method for directly preparing nickel sulfate by using low-nickel matte, nickel sulfate and application thereof.
  • nickel As a key metal in the production of cathode materials in lithium batteries, nickel is of great strategic significance to promote the healthy and sustainable development of the new energy vehicle technology industry. At present, nickel mainly comes from nickel sulfide ore and laterite nickel ore, and the nickel in laterite nickel ore accounts for more than 60% of the total known nickel in the world. Due to the continuous reduction of nickel sulfide ore production and the increasing demand for nickel in industrial production, laterite nickel ore will gradually become the main source of nickel.
  • the average nickel grade of the proven land-based laterite nickel ore is about 1.3%, and the ore has the characteristics of low nickel, high silicon, high iron-nickel ratio and high magnesium-nickel ratio.
  • the laterite nickel ore is reduced and smelted at high temperature, and the nickel-iron oxide in the laterite nickel ore is reduced to a metallic state, thereby obtaining a low-nickel-containing nickel matte (low-nickel matte), and the mass percentage of nickel in the low-nickel matte is 5-20% , the low-nickel matte is smelted to obtain high-nickel-containing nickel matte (high-nickel matte) through strengthening technology.
  • the mass percentage of nickel in the high-nickel matte is 45-70%.
  • high pressure-normal pressure combined leaching and other methods for leaching, the leached nickel salt, iron salt, and calcium salt are separated and extracted by ion exchange or solvent extraction.
  • the remaining Acid is neutralized.
  • the process is complex and needs to be converted from low-nickel matte to high-nickel matte, and in the process of obtaining high-nickel matte by smelting low-nickel matte, the discharged slag contains nickel and iron, so the low-nickel matte will be wasted 2.
  • the leaching of high-nickel matte a part of nickel and iron are oxidized and transferred to high-silicon slag, which will also be lost; 3.
  • Separation and extraction cannot effectively extract metals from high-concentration acid , the acid neutralization process requires the use of more chemicals, and produces a large amount of harmful inorganic salts to be disposed of.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of method that utilizes low-nickel matte to directly prepare nickel sulfate, and technology is simple, has saved the process that low-nickel matte is obtained high-nickel matte by smelting etc., has saved cost greatly, can avoid this The waste of nickel caused by the process can obtain nickel sulfate with higher purity and increase the recovery of nickel.
  • First aspect of the present invention provides a kind of method utilizing low-nickel matte to directly prepare nickel sulfate, comprises the following steps:
  • the applicant of the present invention found in the research that by cooling the supersaturated sulfate solution to -5 ⁇ 0°C, substances including three forms can be roughly formed after cooling, that is, the sulfuric acid solution will be cooled into ice, sulfuric acid and part of the sulfate The solution remains liquid, with insoluble solids (most of the crystals formed from the sulfate solution and insoluble impurities).
  • the mass transfer process is completely caused by diffusion Controlled; at a certain temperature, when the solution begins to solidify, the aqueous solution tries to condense in the form of pure water, and diffuses the excess solute into the solution in front of the solid-liquid interface to form a sulfate-rich layer.
  • More polymorphic sulfate crystals can be incorporated into insoluble solids by cooling: Since the cooling environment is cooling and crystallizing in an acidic environment, there is no need to dilute with water and dissolve sulfate for extraction, so it can be used in acidic environments , to achieve the purpose of concentrating the sulfate solution, strengthening the continued crystallization of sulfate in acid, which can increase the recovery of nickel and reduce waste, and then through suction filtration, the insoluble solid is separated from the acid solution.
  • the low-nickel matte is a low-nickel matte obtained by reducing and smelting laterite nickel ore; the pretreatment includes: grinding the low-nickel matte with a ball mill to obtain a particle size >200 mesh
  • the ferronickel powder is then put into the heating furnace and dried at a high temperature of 300-650°C for 1-2 hours. During the drying process, the air is kept in contact with the ferronickel powder at high temperature and oxidized to obtain a dry ferronickel powder with a particle size of >200 mesh.
  • the step b) includes: adding the ferronickel powder into a container with an open top, then adding the sulfuric acid solution for mixing, stirring, dissolving, and then evaporating to obtain a supersaturated sulfate solution; the nickel
  • the solid-to-liquid ratio (w/v) of the iron powder and the sulfuric acid solution is 1:(3-10), the molar concentration of the sulfuric acid solution is 0.01-0.08mol/L, and the dissolution temperature is 35-65°C , the evaporation temperature is 100-120° C., the stirring time is 20-60 min, and the supersaturated sulfate solution includes supersaturated nickel sulfate solution, supersaturated iron sulfate solution and supersaturated magnesium sulfate solution.
  • the applicant of the present invention has also found that nickel can be selectively leached by sulfuric acid solution with low molar concentration and low temperature conditions. , through the measurement data, more than 96.4% of the nickel in the ferronickel powder is dissolved in the sulfuric acid solution with low molar concentration, and the amount of nickel remaining in the insoluble slag in the low-nickel matte is only less than 4% of the nickel in the low-nickel matte,
  • the metals in the insoluble slag are mainly iron and magnesium.
  • nickel is leached with a low amount of sulfuric acid, and the leaching amount of impurity metals such as iron, calcium, and magnesium will also be reduced, and the dosage of chemicals can be reduced in subsequent impurity removal, which solves the problem of high chemical consumption in the nickel recovery process. problem, reducing the cost of nickel recovery.
  • the step c) includes: after the supersaturated sulfate solution in the top open container drops to 20-25°C, then cool the supersaturated sulfate solution in the top open container to -5 ⁇ 0°C, remove the upper layer of ice, filter out the unfrozen solution in the middle layer, and obtain the insoluble solid in the bottom layer;
  • the ice layer includes sulfuric acid, and the ice layer is mainly formed by freezing sulfuric acid solution;
  • the unfrozen solution in the middle layer is mainly sulfuric acid And part of the sulfate composition;
  • the insoluble solids include sulfate crystals and some insoluble impurities.
  • the ice layer and the solution filtered by suction can be reused in step b), saving cost.
  • the present invention adopts the top open container, this is because the solution system in the process of freezing into ice, the bottom and four sides of the open container have a certain heat preservation effect, cooling to -5 ⁇ 0 °C, the solution in the open direction can be preferentially cooled To the freezing point and nucleate, freeze, so the upper solution in the container will freeze preferentially, and the bottom and four sides of the open container are not frozen.
  • said step d) includes:
  • the dilute alkali solution includes sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution or barium hydroxide solution, preferably sodium hydroxide solution, and the mole of the dilute alkali solution
  • concentration is 0.01-0.2mol/L
  • pH of the mixed reaction solution is 2.0-3.5
  • potential of the filtrate is controlled at 0.25-0.4V
  • reaction temperature is 60-95°C.
  • the step d1) further includes: aging for 3-15 hours after the mixing reaction.
  • the dilute alkali solution includes sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution or barium hydroxide solution, preferably sodium hydroxide solution, and the mole of the dilute alkali solution
  • concentration is 0.01-0.2mol/L
  • the fluoride salt includes sodium fluoride or potassium fluoride
  • the pH of the mixed reaction solution is 4.8-5.5
  • the molar concentration ratio is 1:1.5-5
  • the reaction temperature is 60-95°C.
  • the step d2) further includes: aging for 3-15 hours after the mixing reaction.
  • the dilute alkali solution includes sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution or barium hydroxide solution, preferably sodium hydroxide solution, and the mole of the dilute alkali solution
  • the concentration is 0.01-0.2 mol/L; the pH of the mixed reaction solution is 7.0-8.5.
  • the step e includes: adding water at a temperature of 60-95°C to the nickel hydroxide precipitation to wash the impurities, adding 0.01-0.1 mol/L dilute sulfuric acid solution to dissolve the nickel hydroxide obtained by filtration, and obtaining sulfuric acid nickel solution, and then the nickel sulfate solution is evaporated to obtain the nickel sulfate.
  • the second aspect of the present invention provides a kind of nickel sulfate, which is prepared by using the method of the present invention to directly prepare nickel sulfate using low-nickel matte.
  • the third aspect of the present invention provides the application of said nickel sulfate in batteries, preferably in lithium batteries.
  • the method of the present invention utilizes low-nickel matte to directly prepare nickel sulfate, the process is simple, and the process of obtaining high-nickel matte by melting the low-nickel matte is omitted, which greatly saves the cost and can avoid the waste of nickel caused by the process.
  • the nickel sulfate with higher purity can be obtained, and the recovery amount of nickel is increased.
  • the purity of the nickel sulfate is 18.10-19.24% in terms of nickel, and the recovery rate is 94.8-97.1%.
  • Figure 1 is a schematic flow diagram of the method for directly preparing nickel sulfate by using low-nickel matte in Example 1 of the present invention.
  • Fig. 2 is the SEM picture of the low-nickel matte of Example 1 of the present invention.
  • the components, reagents or devices used in the following examples can be obtained from conventional commercial channels, or can be obtained by existing known methods.
  • Figure 1 is a schematic process flow diagram of the method for directly preparing nickel sulfate using low-nickel matte in this embodiment.
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • ferronickel powder into an open container at the top, add sulfuric acid solution with a molar concentration of 0.01mol/L according to the solid-to-liquid ratio (w/v) of 1:6, mix, stir at 35°C for 40min, and dissolve Then evaporate at 107°C to obtain supersaturated sulfate solutions such as supersaturated nickel sulfate solution, supersaturated ferric sulfate solution and supersaturated magnesium sulfate solution;
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • ferronickel powder into an open container at the top, add sulfuric acid solution with a molar concentration of 0.04mol/L according to the solid-to-liquid ratio (w/v) of 1:4.5 and mix, stir at 46°C for 20min, dissolve Then evaporate at 105°C to obtain supersaturated sulfate solutions such as supersaturated nickel sulfate solution, supersaturated ferric sulfate solution and supersaturated magnesium sulfate solution;
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • the low-nickel matte obtained by reducing and smelting lateritic nickel ore is ground by a ball mill to obtain nickel-iron powder with a particle size >200 mesh, and then put into a heating furnace and dried at a high temperature of 450°C for 1.5 hours. During the drying process, air and nickel are kept The iron powder is contacted and oxidized at high temperature to obtain dry 5.5kg ferronickel powder;
  • Embodiment 4 (the difference with embodiment 1 is that the sulfuric acid solution molar concentration of step b) is higher)
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • the low-nickel matte obtained by reducing and smelting lateritic nickel ore is ground by a ball mill to obtain nickel-iron powder with a particle size >200 mesh, and then put into a heating furnace and dried at a high temperature of 450°C for 1.5 hours. During the drying process, air and nickel are kept The iron powder is contacted and oxidized at high temperature to obtain dry 3.5kg ferronickel powder;
  • ferronickel powder into an open container at the top, add sulfuric acid solution with a molar concentration of 0.1mol/L according to the solid-to-liquid ratio (w/v) of 1:6, mix, stir at 35°C for 40min, and dissolve Then evaporate at 107°C to obtain supersaturated sulfate solutions such as supersaturated nickel sulfate solution, supersaturated ferric sulfate solution and supersaturated magnesium sulfate solution;
  • Embodiment 5 (the difference with embodiment 1 is that the dissolution temperature of step b) is higher)
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • the low-nickel matte obtained by reducing and smelting lateritic nickel ore is ground by a ball mill to obtain nickel-iron powder with a particle size >200 mesh, and then put into a heating furnace and dried at a high temperature of 450°C for 1.5 hours. During the drying process, air and nickel are kept The iron powder is contacted and oxidized at high temperature to obtain dry 3.5kg ferronickel powder;
  • ferronickel powder into an open container at the top, add sulfuric acid solution with a molar concentration of 0.01mol/L according to the solid-to-liquid ratio (w/v) of 1:6, mix, stir at 35°C for 40min, and dissolve Then evaporate at 107°C to obtain supersaturated sulfate solutions such as supersaturated nickel sulfate solution, supersaturated ferric sulfate solution and supersaturated magnesium sulfate solution;
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • the low-nickel matte obtained by reducing and smelting lateritic nickel ore is ground by a ball mill to obtain nickel-iron powder with a particle size >200 mesh, and then put into a heating furnace and dried at a high temperature of 450°C for 1.5 hours. During the drying process, air and nickel are kept The iron powder is contacted and oxidized at high temperature to obtain dry 3.5kg ferronickel powder;
  • ferronickel powder into an open container at the top, add sulfuric acid solution with a molar concentration of 0.01mol/L according to the solid-to-liquid ratio (w/v) of 1:6, mix, stir at 35°C for 40min, and dissolve Then evaporate at 105°C to obtain supersaturated sulfate solutions such as supersaturated nickel sulfate solution, supersaturated ferric sulfate solution and supersaturated magnesium sulfate solution;
  • a kind of method utilizing low-nickel matte to directly prepare nickel sulfate comprises the following steps:
  • the low-nickel matte obtained by reducing and smelting lateritic nickel ore is ground by a ball mill to obtain nickel-iron powder with a particle size >200 mesh, and then put into a heating furnace and dried at a high temperature of 450°C for 1.5 hours. During the drying process, air and nickel are kept The iron powder is contacted and oxidized at high temperature to obtain dry 3.5kg ferronickel powder;
  • ferronickel powder into an open container at the top, add sulfuric acid solution with a molar concentration of 0.01mol/L according to the solid-to-liquid ratio (w/v) of 1:6, mix, stir at 35°C for 40min, and dissolve Then evaporate at 107°C to obtain supersaturated sulfate solutions such as supersaturated nickel sulfate solution, supersaturated ferric sulfate solution and supersaturated magnesium sulfate solution;
  • the purity of the nickel sulfate prepared by the embodiment of the present invention 1-5 is respectively 18.76%, 19.24%, 18.93%, 18.35%, 18.10% in terms of nickel, while the purity of the nickel sulfate prepared by comparative example 1-2 is The purity is respectively 16.96% and 17.73% in terms of nickel, and the purity of the nickel sulfate prepared in Example 1-5 is obviously higher than that in Comparative Example 1-2. Simultaneously the rate of recovery of the nickel sulfate of embodiment 1-5 is also obviously higher than the rate of recovery of comparative example 1-2.
  • embodiment 4-5 are all lower than embodiment 1-3, illustrate that the present invention can selectively leach nickel by utilizing the sulfuric acid solution of low molar concentration and low temperature condition, further improve the purity and the recovery rate of nickel sulfate .

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Abstract

本发明属于湿法冶金技术领域，公开了一种利用低镍锍直接制备硫酸镍的方法、硫酸镍及其应用，该方法包括以下步骤：a)将低镍锍进行预处理，得到镍铁粉；b)将镍铁粉和硫酸溶液混合，搅拌，溶解，再经过蒸发，得到过饱和硫酸盐溶液；c)将过饱和硫酸盐溶液冷却至-5～0℃，抽滤，得到不溶固体；d)将不溶固体水洗，对滤液进行除杂，得到氢氧化镍沉淀；除杂包括依次进行：脱除铁，脱除钙、镁；e)对氢氧化镍沉淀进行水洗、酸溶、蒸发，得到硫酸镍。本发明可直接制备硫酸镍，避免造成镍的浪费，同时能够得到纯度较高的硫酸镍，提高镍的回收量，硫酸镍纯度以镍计为18.10～19.24％，回收率为94.8～97.1％。

Description

一种利用低镍锍直接制备硫酸镍的方法、硫酸镍及其应用 技术领域
本发明属于湿法冶金技术领域，特别涉及一种利用低镍锍直接制备硫酸镍的方法、硫酸镍及其应用。
背景技术
镍作为生产锂电池中正极材料的关键金属，对推动新能源汽车技术产业的健康、可持续发展具有重要的战略意义。目前，镍主要来源于硫化镍矿和红土镍矿，其中红土镍矿中的镍占全世界已知镍总量的60％以上。由于硫化镍矿产量的持续减少，同时伴随着工业生产对镍需求量的不断增加，红土镍矿将逐渐成为镍的主要来源。
当前，探明的陆基红土镍矿平均镍品位在1.3％左右，矿品具有低镍、高硅、高铁镍比和高镁镍比的特点。火法冶金和湿法冶金联合提炼红土镍矿中镍的技术，此方法镍、铁、镁的回收率高，是回收镍的主流方法。首先，高温还原熔炼红土镍矿，红土镍矿中镍铁氧化物被还原成金属态，从而得到含低镍的镍锍(低镍锍)，低镍锍中镍的质量百分比为5～20％，低镍锍通过强化技术，熔炼得到含高镍的镍锍(高镍锍)，高镍锍中镍的质量百分比为45～70％，高镍琉常以加压酸浸、常压酸浸或者高压-常压联合浸出等方法进行浸出，浸出出来的镍盐、铁盐、钙盐通过离子交换或溶剂萃取法分离提取，同时，镍盐、铁盐、钙盐分离之前，需要对剩余的酸进行中和。但上述步骤存在以下不足：1、工艺复杂，需要由低镍锍转变为高镍锍，且低镍锍熔炼得到高镍锍过程中，排出的炉渣含有镍、铁，因此会浪费掉低镍锍中的部分镍；2、高镍锍在浸出时，一部分的镍、铁被氧化转入到高硅矿渣中，也将损失掉；3、分离提取并不能从高浓度的酸中有效地提取金属，酸中和过程中需要使用较多的药剂，产生大量有害的无机盐要被处理。
发明内容
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，本发明提出一种利用低镍锍直接制备硫酸镍的方法，工艺简单，省去了将低镍锍通过熔炼等得到高镍锍的过程，极大的节约了成本，同时可避免该过程造成镍的浪费，能够得到纯度较高的硫酸镍，提高镍 的回收量。
本发明的第一方面提供一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将低镍锍进行预处理，得到镍铁粉；
b)将所述镍铁粉和硫酸溶液混合，搅拌，溶解，再经过蒸发，得到过饱和硫酸盐溶液；
c)将所述过饱和硫酸盐溶液冷却至-5～0℃，抽滤，得到不溶固体；
d)将所述不溶固体溶解，对滤液进行除杂，得到氢氧化镍沉淀；所述除杂包括依次进行：脱除铁，脱除钙、镁；
e)对所述氢氧化镍沉淀进行水洗、酸溶、蒸发，得到所述硫酸镍。
本发明申请人在研究中发现，通过对过饱和硫酸盐溶液进行冷却至-5～0℃，经过冷却可大致形成包括三种形态的物质，即硫酸溶液会冷却成冰、硫酸以及部分硫酸盐溶液保持液体状态、不溶固体(大部分硫酸盐溶液形成的结晶体以及不溶杂质)。通过冷却，硫酸溶液以及水会冷却成冰，但较多的硫酸盐的存在会扰乱硫酸盐溶液中水的晶格结构，使其不能达到较低能级，把多余的硫酸盐排到未冻结的硫酸盐溶液中，形成硫酸盐富集溶液，其原因是：在无外力搅拌，晶体的生长速率较低时，液相中的流动非常弱，因此，可以认为质量传递过程中完全是由扩散控制的；在一定温度下，当溶液开始凝固时，水溶液极力以纯水的形式凝结，而把多余的溶质扩散到固-液界面前面的溶液中，形成硫酸盐富集层。通过冷却可以将更多的多态硫酸盐结晶并入到不溶固体中：由于降温的环境是在酸环境下降温结晶的，不需用水进行稀释并溶出硫酸盐进行提取，因此能在酸环境下，达到浓缩硫酸盐溶液的目的，强化硫酸盐在酸中继续结晶，能够提高镍的回收量，减少浪费，然后再通过抽滤，使得不溶固体与酸溶液分离。
优选地，所述步骤a)中，所述低镍锍为红土镍矿还原熔炼得来的低镍锍；所述预处理包括：将所述低镍锍采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温300～650℃下干燥1～2h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到粒度>200目、干燥的镍铁粉。
优选地，所述步骤b)包括：将所述镍铁粉加入顶部敞口容器中，再加入所述硫酸溶液进行混合，搅拌，溶解，再经过蒸发，得到过饱和硫酸盐溶液；所述镍铁粉和所述硫酸溶液的固液比(w/v)为1：(3～10)，所述硫酸溶液的摩尔浓度为0.01～0.08mol/L，所述溶解的 温度为35～65℃，所述蒸发的温度为100～120℃，所述搅拌的时间为20～60min，所述过饱和硫酸盐溶液包括过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液。
除了对过饱和硫酸盐溶液进行冷却至-5～0℃对镍的回收量的提高有影响之外，本发明申请人还发现，利用低摩尔浓度的硫酸溶液以及低温条件可以选择性地浸出镍，通过测定数据，镍铁粉中96.4％以上的镍溶解到低摩尔浓度的硫酸溶液中，低镍锍中的镍残留在不溶渣中的量仅占低镍锍中不到4％的镍，不溶渣中金属以铁、镁为主。因此实现了利用低量的硫酸来浸出镍，同样铁、钙、镁等杂质金属的浸出量也将减少，后续除杂时能够减少药剂用量，很好地解决了镍回收过程中药剂消耗高的问题，降低了镍的回收成本。
优选地，所述步骤c)包括：待所述顶部敞口容器中的过饱和硫酸盐溶液降至20～25℃，再将所述顶部敞口容器中的过饱和硫酸盐溶液冷却至-5～0℃，除去上层的冰层，抽滤掉中层未冻结的溶液，得到底层的不溶固体；所述冰层包括硫酸，冰层主要为硫酸溶液冻结而成；中层未冻结的溶液主要是硫酸以及部分硫酸盐组成；所述不溶固体包括硫酸盐晶体和一些不溶杂质。其中冰层和抽滤掉的溶液可回用于步骤b)中，节约成本。
本发明采用顶部敞口容器，这是因为溶液体系在冷冻成冰的过程中，敞口容器的底部和四面有一定保温作用，降温至-5～0℃，敞口方向的溶液能够优先过降温至冰点并成核、结冰，因此容器中的上层溶液会优先进行结冰，敞口容器的底部和四面并未结冰。
优选地，所述步骤d)包括：
d1)将所述不溶固体加水水洗，除去不溶渣，得到滤液；所述不溶固体和所述水的固液比(w/v)为1：(4～8)，所述水洗的温度为60～95℃；将所述滤液和稀碱溶液混合反应，再进行固液分离，得到除铁后液；
d2)将所述除铁后液和稀碱溶液、氟盐混合反应，再进行固液分离，得到除钙、镁后液；
d3)将所述除钙、镁后液和稀碱溶液混合反应，再进行固液分离，得到所述氢氧化镍沉淀。
优选地，所述步骤d1)中，所述稀碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液或氢氧化钡溶液，优选为氢氧化钠溶液，所述稀碱溶液的摩尔浓度为0.01～0.2mol/L；混合反应溶液的pH为2.0～3.5；所述滤液的电位控制在0.25～0.4V；所述反应的温度为60～95℃。
优选地，所述步骤d1)中，还包括：在所述混合反应后，陈化3～15h。
优选地，所述步骤d2)中，所述稀碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液或氢氧化钡溶液，优选为氢氧化钠溶液，所述稀碱溶液的摩尔浓度为0.01～0.2mol/L；所述氟盐包括氟化钠或氟化钾；混合反应溶液的pH为4.8～5.5；混合反应溶液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：1.5～5；所述反应的温度为60～95℃。
优选地，所述步骤d2)中，还包括：在所述混合反应后，陈化3～15h。
优选地，所述步骤d3)中，所述稀碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液或氢氧化钡溶液，优选为氢氧化钠溶液，所述稀碱溶液的摩尔浓度为0.01～0.2mol/L；混合反应溶液的pH为7.0～8.5。
优选地，所述步骤e包括：往所述氢氧化镍沉淀加入温度为60～95℃的水进行水洗杂质，过滤得到的氢氧化镍加0.01～0.1mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，再将硫酸镍溶液蒸发，得到所述硫酸镍。
本发明的第二方面提供一种硫酸镍，其采用本发明所述的利用低镍锍直接制备硫酸镍的方法制得。
本发明的第三方面提供所述的硫酸镍在电池中的应用，优选在锂电池中的应用。
相对于现有技术，本发明的有益效果如下：
本发明利用低镍锍直接制备硫酸镍的方法，工艺简单，省去了将低镍锍通过熔炼等得到高镍锍的过程，极大的节约了成本，可避免该过程造成镍的浪费，同时能够得到纯度较高的硫酸镍，提高镍的回收量，硫酸镍纯度以镍计为18.10～19.24％，回收率为94.8～97.1％。
附图说明
图1为本发明实施例1利用低镍锍直接制备硫酸镍的方法的流程示意图。
图2为本发明实施例1的低镍锍的SEM图。
具体实施方式
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举如下实施例进行说明。需要指出的是，如下实施例对本发明要求的保护范围不构成限制作用。
如下实施例中所用的组分、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。
实施例1
工艺流程参照图1，图1为本实施例利用低镍锍直接制备硫酸镍的方法的工艺流程示意图。
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.5h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的3.5kg镍铁粉；参照图2，图2为低镍锍的SEM(扫描电子显微镜)图，从图中可以看出低镍锍是破碎颗粒状，部分为柱状。
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：6加入摩尔浓度为0.01mol/L的硫酸溶液进行混合，在35℃条件下搅拌40min，溶解后再在107℃条件下进行蒸发，得到过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至22℃，再将顶部敞口容器中的过饱和硫酸盐溶液冷却至-3℃，除去上层的冰层，抽滤掉未冻结的溶液，得到不溶固体；冰层包括硫酸，不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：5.5，将不溶固体加温度为80℃的水进行水洗，除去不溶渣，得到滤液；往滤液中加入0.1mol/L的氢氧化钠溶液直至pH为2.7，电位控制在0.36V，在温度为84℃下进行沉淀反应，陈化8h，除去沉淀物质(氢氧化铁，回收铁)，得到除铁后液；
往除铁后液中加入0.1mol/L的氢氧化钠溶液和氟化钠，直至pH为5.4，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：2，在温度为65℃下进行沉淀反应，陈化8h，除去沉淀物质(氟化钙、氟化镁，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.1mol/L的氢氧化钠溶液直至pH为8.4，抽滤掉溶液，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.5加入温度为85℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.01mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
实施例2
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.25h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的4.6kg镍铁粉；
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：4.5加入摩尔浓度为0.04mol/L的硫酸溶液进行混合，在46℃条件下搅拌20min，溶解后再在105℃条件下进行蒸发，得到过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至20℃，再将顶部敞口容器中的过饱和硫酸盐溶液冷却至-5℃，除去上层的冰层，抽滤掉未冻结的溶液，得到不溶固体；冰层包括硫酸，不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：6，将不溶固体加温度为65℃的水进行水洗，除去不溶渣，得到滤液；往滤液中加入0.01mol/L的氢氧化钠溶液直至pH为3.1，电位控制在0.28V，在温度为80℃下进行沉淀反应，陈化3h，除去沉淀物质(氢氧化铁，回收铁)，得到除铁后液；
往除铁后液中加入0.01mol/L的氢氧化钠溶液和氟化钠，直至pH为4.9，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：2.5，在温度为60℃下进行沉淀反应，陈化3h，除去沉淀物质(氟化钙、氟化镁，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.01mol/L的氢氧化钠溶液直至pH为7.7，抽滤，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.5加入温度为80℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.04mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
实施例3
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.5h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的5.5kg镍铁粉；
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：8加入摩尔浓度为0.05mol/L的硫酸溶液进行混合，在43℃条件下搅拌60min，溶解后再在120℃条件下进行蒸发，得到 过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至25℃，再将顶部敞口容器中的过饱和硫酸盐溶液冷却至-1℃，除去上层的冰层，抽滤掉未冻结的溶液，得到不溶固体；冰层包括硫酸，不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：5.5，将不溶固体加温度为95℃的水进行水洗，除去不溶渣，得到滤液；往滤液中加入0.2mol/L的氢氧化钠溶液直至pH为3.4，电位控制在0.39V，在温度为84℃下进行沉淀反应，陈化12h，除去沉淀物质(氢氧化铁，回收铁)，得到除铁后液；
往除铁后液中加入0.2mol/L的氢氧化钠溶液和氟化钠，直至pH为5.5，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：1.8，在温度为95℃下进行沉淀反应，陈化12h，除去沉淀物质(氟化钙、氟化镁，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.2mol/L的氢氧化钠溶液直至pH为8.5，抽滤，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.2加入温度为78℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.05mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
实施例4(与实施例1的区别在于步骤b)的硫酸溶液摩尔浓度较高)
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.5h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的3.5kg镍铁粉；
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：6加入摩尔浓度为0.1mol/L的硫酸溶液进行混合，在35℃条件下搅拌40min，溶解后再在107℃条件下进行蒸发，得到过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至22℃，再将顶部敞口容器中的过饱和硫酸盐溶液冷却至-3℃，除去上层的冰层，抽滤掉未冻结的溶液，得到不溶固体；冰层包括硫酸，不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：5.5，将不溶固体加温度为80℃的水进行水洗，除去不溶渣， 得到滤液；往滤液中加入0.1mol/L的氢氧化钠溶液直至pH为2.7，电位控制在0.36V，在温度为84℃下进行沉淀反应，陈化8h，除去沉淀物质(氢氧化铁，回收铁)，得到除铁后液；
往除铁后液中加入0.1mol/L的氢氧化钠溶液和氟化钠，直至pH为5.4，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：2，在温度为65℃下进行沉淀反应，陈化8h，除去沉淀物质(氟化钙、氟化镁，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.1mol/L的氢氧化钠溶液直至pH为8.4，抽滤掉溶液，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.5加入温度为85℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.01mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
实施例5(与实施例1的区别在于步骤b)的溶解温度较高)
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.5h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的3.5kg镍铁粉；
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：6加入摩尔浓度为0.01mol/L的硫酸溶液进行混合，在35℃条件下搅拌40min，溶解后再在107℃条件下进行蒸发，得到过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至22℃，再将顶部敞口容器中的过饱和硫酸盐溶液冷却至-3℃，除去上层的冰层，抽滤掉未冻结的溶液，得到不溶固体；冰层包括硫酸，不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：5.5，将不溶固体加温度为80℃的水进行水洗，除去不溶渣，得到滤液；往滤液中加入0.1mol/L的氢氧化钠溶液直至pH为2.7，电位控制在0.36V，在温度为84℃下进行沉淀反应，陈化8h，除去沉淀物质(氢氧化铁，回收铁)，得到除铁后液；
往除铁后液中加入0.1mol/L的氢氧化钠溶液和氟化钠，直至pH为5.4，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：2，在温度为65℃下进行沉淀反应，陈化8h，除去沉淀物质(氟化钙、氟化镁，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.1mol/L的氢氧化钠溶液直至pH为8.4，抽滤掉溶液，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.5加入温度为85℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.01mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
对比例1(与实施例1的区别在于步骤c)未进行冷却处理)
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.5h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的3.5kg镍铁粉；
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：6加入摩尔浓度为0.01mol/L的硫酸溶液进行混合，在35℃条件下搅拌40min，溶解后再在105℃条件下进行蒸发，得到过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至22℃，抽滤掉溶液，得到不溶固体；不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：5.5，将不溶固体加温度为80℃的水进行水洗，除去不溶渣，得到滤液；往滤液中加入0.1mol/L的氢氧化钠溶液直至pH为2.7，电位控制在0.36V，在温度为84℃下进行沉淀反应，陈化8h，除去沉淀物质(氢氧化铁，回收铁)，得到除铁后液；
往除铁后液中加入0.1mol/L的氢氧化钠溶液和氟化钠，直至pH为8.4，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：2，在温度为65℃下进行沉淀反应，陈化8h，除去沉淀物质(氢氧化镁、氢氧化钙，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.1mol/L的氢氧化钠溶液直至pH为8.4，抽滤，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.5加入温度为85℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.01mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
对比例2(与实施例1的区别在于步骤c)冷却处理的温度偏高)
一种利用低镍锍直接制备硫酸镍的方法，包括以下步骤：
a)将红土镍矿还原熔炼得来的低镍锍，采用球磨机进行研磨，得到粒度>200目的镍铁粉，然后加入加热炉内，在高温450℃下干燥1.5h，干燥过程保持空气与镍铁粉在高温下接触并氧化，得到干燥的3.5kg镍铁粉；
b)将镍铁粉加入顶部敞口容器中，按照固液比(w/v)为1：6加入摩尔浓度为0.01mol/L的硫酸溶液进行混合，在35℃条件下搅拌40min，溶解后再在107℃条件下进行蒸发，得到过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液等过饱和硫酸盐溶液；
c)待顶部敞口容器中的过饱和硫酸盐溶液降至22℃，再将顶部敞口容器中的过饱和硫酸盐溶液降温至1℃，抽滤掉溶液，得到不溶固体；不溶固体包括硫酸盐晶体；
d)按照固液比(w/v)为1：5.5，将不溶固体加温度为80℃的水进行水洗，除去不溶渣，得到滤液；往滤液中加入0.1mol/L的氢氧化钠溶液直至pH为2.8，电位控制在0.31V，在温度为84℃下进行沉淀反应，陈化8h，除去沉淀物质(氢氧化铁、，回收铁)，得到除铁后液；
往除铁后液中加入0.1mol/L的氢氧化钠溶液和氟化钠，直至pH为5.4，混合液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：2，在温度为65℃下进行沉淀反应，陈化10h，除去沉淀物质(氟化镁、氟化钙，回收镁、钙)，得到除钙、镁后液；
往除钙、镁后液中加入0.1mol/L的氢氧化钠溶液直至pH为8.4，抽滤，得到氢氧化镍沉淀。
e)往氢氧化镍沉淀中按照固液比(w/v)1：1.5加入温度为85℃的水，进行水洗除去杂质，过滤得到的氢氧化镍沉淀再加0.01mol/L的稀硫酸溶液溶解，得到硫酸镍溶液，然后将硫酸镍溶液蒸发，得到硫酸镍。
分别对实施例1-5以及对比例1-2制备过程中的元素质量含量及镍利用ICP-OES进行检测，并计算镍的回收率，结果见表1所示。
表1实施例1-5以及对比例1-2各元素百分比以及镍的回收率
Figure PCTCN2022096308-appb-000001
Figure PCTCN2022096308-appb-000002
Figure PCTCN2022096308-appb-000003
由表1可知，本发明实施例1-5制备的硫酸镍的纯度，以镍计分别为18.76％、19.24％、18.93％、18.35％、18.10％，而对比例1-2制备的硫酸镍的纯度，以镍计分别为16.96％、17.73％，实施例1-5制备的硫酸镍的纯度明显高于对比例1-2的纯度。同时实施例1-5的硫酸镍的回收率也明显高于对比例1-2的回收率。实施例4-5的纯度及回收率均偏低于实施例1-3，说明本发明通过利用低摩尔浓度的硫酸溶液以及低温条件可以选择性地浸出镍，进一步提高硫酸镍的纯度及回收率。
以上对本发明的较佳实施方式进行了具体说明，但本发明创造并不限于所述实施例，熟悉本领域的技术人员在不违背本发明精神的前提下还可作出种种的等同变型或替换，这些等同的变型或替换均包含在本申请权利要求所限定的范围内。

Claims (10)

  1. 一种利用低镍锍直接制备硫酸镍的方法，其特征在于，包括以下步骤：
    a)将低镍锍进行预处理，得到镍铁粉；
    b)将所述镍铁粉和硫酸溶液混合，搅拌，溶解，再经过蒸发，得到过饱和硫酸盐溶液；
    c)将所述过饱和硫酸盐溶液冷却至-5～0℃，抽滤，得到不溶固体；
    d)将所述不溶固体溶解，对滤液进行除杂，得到氢氧化镍沉淀；所述除杂包括依次进行：脱除铁，脱除钙、镁；
    e)对所述氢氧化镍沉淀进行水洗、酸溶、蒸发，得到所述硫酸镍。
  2. 根据权利要求1所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤a)中，所述低镍锍中镍的质量百分比为5～20％；所述预处理包括：将所述低镍锍进行研磨，干燥，得到粒度>200目的镍铁粉。
  3. 根据权利要求1所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤b)包括：将所述镍铁粉加入敞口容器中，再加入所述硫酸溶液进行混合，搅拌，溶解，再经过蒸发，得到过饱和硫酸盐溶液；所述镍铁粉和所述硫酸溶液的固液比(w/v)为1：(3～10)，所述硫酸溶液的摩尔浓度为0.01～0.08mol/L，所述溶解的温度为35～65℃，所述蒸发的温度为100～120℃，所述搅拌的时间为20～60min，所述过饱和硫酸盐溶液包括过饱和硫酸镍溶液、过饱和硫酸铁溶液和过饱和硫酸镁溶液。
  4. 根据权利要求3所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤c)包括：待所述敞口容器中的过饱和硫酸盐溶液降至20～25℃，再将所述敞口容器中的过饱和硫酸盐溶液冷却至-5～0℃，除去冰层，抽滤掉溶液，得到不溶固体；所述冰层包括硫酸，所述不溶固体包括硫酸盐晶体。
  5. 根据权利要求1所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤d)包括：
    d1)将所述不溶固体加水水洗，除去不溶渣，得到滤液；所述不溶固体和所述水的固液比(w/v)为1：(4～8)，所述溶解的温度为60～95℃；将所述滤液和稀碱溶液混合反应，再进行固液分离，得到除铁后液；
    d2)将所述除铁后液和稀碱溶液、氟盐混合反应，再进行固液分离，得到除钙、镁后液；
    d3)将所述除钙、镁后液和稀碱溶液混合反应，再进行固液分离，得到所述氢氧化镍沉淀。
  6. 根据权利要求5所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤d1)中，所述稀碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液或氢氧化钡溶液，所述稀碱溶液的摩尔浓度为0.01～0.2mol/L；混合反应溶液的pH为2.0～3.5；所述滤液的电位控制在0.25～0.4V；所述反应的温度为60～95℃。
  7. 根据权利要求5所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤d2)中，所述稀碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液或氢氧化钡溶液，所述稀碱溶液的摩尔浓度为0.01～0.2mol/L；所述氟盐包括氟化钠或氟化钾；混合反应溶液的pH为4.8～5.5；混合反应溶液中镁离子和钙离子的摩尔浓度之和与氟离子的摩尔浓度比为1：1.5～5；所述反应的温度为60～95℃。
  8. 根据权利要求5所述的利用低镍锍直接制备硫酸镍的方法，其特征在于，所述步骤d3)中，所述稀碱溶液包括氢氧化钠溶液、氢氧化钾溶液、氢氧化锂溶液或氢氧化钡溶液，所述稀碱溶液的摩尔浓度为0.01～0.2mol/L；混合反应溶液的pH为7.0～8.5。
  9. 一种硫酸镍，其特征在于，采用权利要求1～8任一项所述的利用低镍锍直接制备硫酸镍的方法制得。
  10. 权利要求9所述的硫酸镍在电池中的应用。
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