WO2014000404A1 - Process for recycling rare earths in permanent magnet scrap of electronic waste - Google Patents
Process for recycling rare earths in permanent magnet scrap of electronic waste Download PDFInfo
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- WO2014000404A1 WO2014000404A1 PCT/CN2012/087752 CN2012087752W WO2014000404A1 WO 2014000404 A1 WO2014000404 A1 WO 2014000404A1 CN 2012087752 W CN2012087752 W CN 2012087752W WO 2014000404 A1 WO2014000404 A1 WO 2014000404A1
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- rare earth
- waste
- chloride
- cobalt
- nickel
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Classifications
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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
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B59/00—Obtaining rare earth metals
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
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- 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 relates to an electronic waste recycling process, in particular to a process for recovering rare earth in an electronic waste permanent magnet waste.
- the electronic waste contains a large amount of permanent magnet materials containing rare earth elements, such as acoustic speakers, rare earth permanent magnet motors widely used in home appliances such as air conditioners and refrigerators, computer hard disk drives, computer magneto-optical disks, etc., whose main component is NdFeB. , samarium and cobalt, etc., which mainly contain rare earth elements such as lanthanum, cerium and lanthanum.
- the rare earths recovered can not only promote the comprehensive utilization of resources, but also reduce the environmental damage of these wastes.
- Rare earth magnetic materials are generally concentrated on some components of electronic products, such as motors for computer hard disk drives, magnetic bodies for rare earth permanent magnet motors, etc., so these magnetic materials are first removed and collected centrally, and then concentrated for processing. Recover rare earth and other valuable metals such as cobalt and nickel.
- the invention provides a process for recovering rare earth in permanent waste of electronic waste in order to solve the problem of pollution of electronic waste and waste of rare earth resources in permanent magnet materials.
- the process for recovering rare earth in the electronic waste permanent magnet waste of the present invention comprises the following steps:
- chlorine gas is introduced and chlorinated by adding carbon powder; or hydrogen chloride is added and chlorinated by adding carbon powder; or chlorination is carried out by adding sodium chloride and carbon powder; or chlorination is carried out by adding calcium chloride and carbon powder.
- the mass ratio of the alloy particles to the chlorine gas and the carbon powder is 1:0.2 to 0.6:2 to 4
- hydrogen chloride is added or other chloride is added
- the mass ratio of alloy particles to chloride to carbon powder is 1:0.2 to 0.6:2 to 4
- the baking time is 2 to After 5 hours, the generated tail gas is absorbed by alkali solution or water spray;
- step (2) The chlorinated calcined powder of step (2) is washed with hot dilute hydrochloric acid in a two-stage countercurrent to dissolve soluble metal chloride salt, solid-liquid ratio 1:4 ⁇ 8 , the filtrate and the filter residue are obtained by filtration, and the filter residue is returned to roasting;
- step (4) adjusting the pH of the filtrate obtained in step (4) to 1.5 to 2.5
- hydrogen sulfide gas is introduced to precipitate all the cobalt nickel, and the pH of the solution is adjusted to 3.3 to 3.7, and the iron ions are removed by precipitation; Pr, Nd, and P517 or P204 are separated and separated.
- cobalt sulfide nickel slag is calcined by sulphation, and after acid dissolution, use P507 or P204 or Cyanex272 Extraction and separation of cobalt nickel and recovery of cobalt nickel.
- the step (1) of the electronic waste permanent magnet waste in the 800 ⁇ 1500 Oxidation at high temperature °C into alloy particles and grinding, grinding to the particles can pass through 60 ⁇ 80 mesh sieve.
- step (2) the mass ratio of the alloy particles to the chloride to the carbon powder is 1:0.4:3, and the baking time is 3 to 4 In an hour, the produced tail gas is sprayed and absorbed with an alkali solution of 2 to 10 mol/l.
- the hot dilute hydrochloric acid in the step (4) is a concentration of 0.1 to 0.3 mol/l at 35 to 65 °C. Hydrochloric acid.
- the solid-liquid ratio in the step (4) is 1:5 to 6.
- Step (5) When the iron ions are precipitated, the pH of the solution is adjusted to 3.4 to 3.6.
- the invention can recover the rare earth in the permanent waste material of the electronic waste well, can solve the problem of the pollution of the electronic waste, and extract the rare earth element in the permanent magnet material, realizes the comprehensive utilization of resources and saves resources.
- the electronic waste permanent magnet waste is oxidized and oxidized at 1500 °C into alloy particles and ground, and the particles can pass through 100. Screen.
- Steps (2) The boron chloride gas in the alkali solution is sprayed and absorbed, and the solution is a mixed solution of borate and chloride salt. After multi-step recrystallization, the borate and the chloride salt are separately recovered, and the borate can be directly sold. The chloride salt is returned to the chlorination roasting.
- Step (2) of the chlorinated calcined powder with hot dilute hydrochloric acid (temperature 65 ° C, concentration 0.1 mol / l)
- the second-stage countercurrent washing dissolves the soluble metal chloride salt, and the solid-liquid ratio is 1:8.
- the filtrate and the filter residue are filtered, and the filter residue is returned to the roasting.
- the filtrate contains a chloride such as rare earth, cobalt or nickel, and also contains a small amount of chloride such as iron. Adjust the pH of the solution to 2.5 At the same time, hydrogen sulfide gas is introduced at the same time to completely precipitate cobalt nickel, and the rare earth ions are all left in the solution, and the pH of the solution is adjusted to 3.7, and the iron ions are removed by precipitation. Extraction and separation of Pr and Nd with P507 , Sm, Dy, etc., obtain Pr, Nd, Sm, Dy rare earth salts with a purity of 99.9%, and then use oxalic acid precipitation roasting to obtain rare earth oxides for sale.
- a chloride such as rare earth, cobalt or nickel
- a small amount of chloride such as iron.
- Adjust the pH of the solution to 2.5
- hydrogen sulfide gas is introduced at the same time to completely precipitate cobalt nickel, and the rare earth ions are all left in the solution, and the pH of the solution
- the cobalt sulfide nickel slag is calcined by sulfation, that is, it is baked at 600 °C for 2 hours under air or oxygen atmosphere, and then used. Dissolve 0.5mol/l sulfuric acid, solid-liquid ratio 1:4, react at 80 °C for 3 hours, use P507 for 12-stage extraction, 10 wash, 6 The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
- the electronic waste permanent magnet waste is oxidized and oxidized at 1000 °C into alloy particles and ground, and the particles can all pass through 80 Screen.
- Steps (2) The boron chloride gas in the alkali solution is sprayed and absorbed, and the solution is a mixed solution of borate and chloride salt. After multi-step recrystallization, the borate and the chloride salt are separately recovered, and the borate can be directly sold. The chloride salt is returned to the chlorination roasting.
- Step (2) of the chlorinated roasting powder with hot dilute hydrochloric acid (temperature 50 ° C, concentration 0.2mol/l) two-stage countercurrent washing, dissolving soluble metal chloride salt, solid-liquid ratio 1:6, filtering to obtain filtrate and filter residue, and returning the filter residue to roasting.
- the filtrate of the step (4) which contains a chloride such as rare earth, cobalt or nickel, and further contains a small amount of chloride such as iron.
- the pH of the solution was adjusted to about 2.2, and hydrogen sulfide gas was introduced to precipitate all the cobalt nickel.
- the rare earth ions were all left in the solution, and the pH of the solution was adjusted to about 3.5, and the iron ions were removed by precipitation.
- Pr, Nd, Sm, Dy, etc. were extracted by P507 to obtain Pr, Nd, Sm and Dy rare earth salts with a purity of 99.9%, and then calcined with oxalic acid to obtain rare earth oxides.
- the cobalt sulfide nickel slag is calcined by sulfation, that is, it is baked at 600 °C for 2 hours under air or oxygen atmosphere, and then used. Dissolve 0.5mol/l sulfuric acid, solid-liquid ratio 1:4, react at 80 °C for 3 hours, use P507 for 12-stage extraction, 10 wash, 6 The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
- the electronic waste permanent magnet waste is oxidized and oxidized at 800 °C into alloy particles and ground, and the particles can all pass 50 Screen.
- Steps (2) The boron chloride gas in the alkali solution is sprayed and absorbed, and the solution is a mixed solution of borate and chloride salt. After multi-step recrystallization, the borate and the chloride salt are separately recovered, and the borate can be directly sold. The chloride salt is returned to the chlorination roasting.
- Step (2) of the chlorinated roasting powder with hot dilute hydrochloric acid (temperature 35 ° C, concentration 0.3 mol/l) two-stage countercurrent washing, dissolving soluble metal chloride salt, solid-liquid ratio 1:4, filtering to obtain filtrate and filter residue, and returning the filter residue to roasting.
- the filtrate of the step (4) which contains a chloride such as rare earth, cobalt or nickel, and further contains a small amount of chloride such as iron.
- the pH of the solution Adjusted to 1.5, while introducing hydrogen sulfide gas, the cobalt nickel is completely precipitated, and the rare earth ions are all left in the solution, and then the pH of the solution is adjusted to about 3.3, and the iron ions are precipitated and removed. Extraction separation with P204 Pr, Nd, Sm, Dy, etc., get Pr, Nd, Sm, Dy rare earth salts with a purity of 99.9%, and then calcined with oxalic acid to obtain rare earth oxides for sale.
- the cobalt sulfide nickel slag is calcined by sulfation, calcined at 600 °C for 2 hours, and then 0.5 mol/l
- the sulfuric acid is dissolved, the solid-liquid ratio is 1:4, the reaction is carried out at 80 °C for 3 hours, and the P204 is subjected to 12-stage extraction, 10 stages of washing, 6 The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
- the electronic waste permanent magnet waste is oxidized at 1200 °C to form alloy particles and ground, and the particles can pass through 70. Screen.
- Steps (2) The boron chloride gas in the water is sprayed and absorbed, and the solution is borate and solution. After multi-step recrystallization, the borate and the chloride salt are separately recovered. The borate can be directly sold, and the chloride salt is returned to the chlorination roasting. .
- the filtrate of the step (4) which contains a chloride such as rare earth, cobalt or nickel, and further contains a small amount of chloride such as iron.
- the pH of the solution Adjusted to 2.5, while introducing hydrogen sulfide gas, the cobalt nickel is completely precipitated, and the rare earth ions are all left in the solution, and then the pH of the solution is adjusted to 3.7, and the iron ions are removed by precipitation. Extraction separation with P507 Pr , Nd, Sm, Dy, etc., get Pr, Nd, Sm, Dy rare earth salts with a purity of 99.9%, and then roast with oxalic acid to obtain rare earth oxides for sale.
- the cobalt sulfide nickel slag is calcined by sulphation, that is, calcined at 600 ° C under air or oxygen atmosphere 2 Hour, then dissolve with 0.5mol/l sulfuric acid, solid-liquid ratio 1:4, react at 80 °C for 3 hours, use P507 for 12-stage extraction, 10 wash, 6 The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
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Abstract
A process for recycling rare earths in permanent magnet scrap of electronic waste comprises: 1) oxidizing and smelting the scrap at a high temperature to obtain alloy particles and levigating the alloy particles; 2) at a high temperature, roasting the alloy particles with a chloride and carbon powder; 3) recycling borates and chlorides with a tail gas absorption liquid through multiple steps of recrystallization; 4) subjecting the powder after chloridizing roasting to two-stage countercurrent washing with hot diluted hydrochloric acid, to dissolve soluble metal chlorides; 5) passing the filtrate through hydrogen sulfide gas under an acid condition so that cobalt and nickel are completely precipitated, and then removing ferric ions by means of precipitation; extracting and separating Pr, Nd, Sm, and Dy, and then precipitating the products with oxalic acid and roasting same to obtain rare earth oxides; 6) subjecting the cobalt and nickel sulfides slag to sulfatizing roasting, after dissolving the product in an acid, extracting and separating cobalt and nickel, and recycling the cobalt and nickel.
Description
本发明涉及电子废弃物回收处理，具体涉及一种电子废弃物永磁废料中回收稀土的工艺。 The invention relates to an electronic waste recycling process, in particular to a process for recovering rare earth in an electronic waste permanent magnet waste.
电子废弃物中含有大量含稀土元素的永磁材料，如音响扬声器、在空调和冰箱等家电上广泛使用的稀土永磁电机、电脑硬盘驱动器、电脑磁光盘等等，其主要成分为钕铁硼、钐钴等，其中主要含有钕、镝、钐等稀土元素，回收其中的稀土不仅能够促进资源的综合利用，还能够减少这些废料对环境的伤害。
The electronic waste contains a large amount of permanent magnet materials containing rare earth elements, such as acoustic speakers, rare earth permanent magnet motors widely used in home appliances such as air conditioners and refrigerators, computer hard disk drives, computer magneto-optical disks, etc., whose main component is NdFeB. , samarium and cobalt, etc., which mainly contain rare earth elements such as lanthanum, cerium and lanthanum. The rare earths recovered can not only promote the comprehensive utilization of resources, but also reduce the environmental damage of these wastes.
在处理这些电子废弃物时，一般先采用人工或者机械拆解，将一些大的零件收集后，集中处理。但这种集中处理的方式往往不利于稀土材料的回收。稀土磁性材料一般比较集中存在于电子产品的某些部件上，比如电脑硬盘驱动器的电机，稀土永磁电机的磁性体等，因此先将这些磁性材料拆下后集中收集，然后再集中处理用以回收稀土和钴、镍等其他有价金属。
When dealing with these e-wastes, they are usually dismantled manually or mechanically, and some large parts are collected and processed centrally. However, this centralized treatment is often not conducive to the recovery of rare earth materials. Rare earth magnetic materials are generally concentrated on some components of electronic products, such as motors for computer hard disk drives, magnetic bodies for rare earth permanent magnet motors, etc., so these magnetic materials are first removed and collected centrally, and then concentrated for processing. Recover rare earth and other valuable metals such as cobalt and nickel.
目前，没有发现关于对电子废弃物永磁废料中回收稀土技术的报道。 At present, no reports have been found on the recovery of rare earth technology in permanent waste of electronic waste.
本发明为解决电子废弃物的污染和永磁材料里稀土资源浪费问题，提供一种电子废弃物永磁废料中回收稀土的工艺。
The invention provides a process for recovering rare earth in permanent waste of electronic waste in order to solve the problem of pollution of electronic waste and waste of rare earth resources in permanent magnet materials.
本发明的电子废弃物永磁废料中回收稀土的工艺，包括以下步骤： The process for recovering rare earth in the electronic waste permanent magnet waste of the present invention comprises the following steps:
（ 1 ）将电子废弃物永磁废料高温氧化熔炼成合金颗粒并磨细，磨至颗粒能够全部过 50 ～ 100
目筛； (1) High-temperature oxidation of permanent waste of electronic waste into alloy particles and grinding, grinding to particles can pass 50 ~ 100
Mesh sieve
（ 2 ）在 800 ～ 1200
℃条件下，通入氯气并加入碳粉氯化焙烧；或通入氯化氢并加入碳粉氯化焙烧；或者加入氯化钠和碳粉氯化焙烧；或者加入氯化钙和碳粉氯化焙烧；当通入氯气时，合金颗粒与氯气与碳粉的质量比为
1:0.2 ～ 0.6:2 ～ 4 ，当通入氯化氢或加入其它氯化物时，合金颗粒与氯化物与碳粉的质量比为 1:0.2 ～ 0.6:2 ～ 4 ，焙烧时间 2 ～
5 小时，产生的尾气采用碱溶液或水喷淋吸收； (2) at 800 to 1200
Under the condition of °C, chlorine gas is introduced and chlorinated by adding carbon powder; or hydrogen chloride is added and chlorinated by adding carbon powder; or chlorination is carried out by adding sodium chloride and carbon powder; or chlorination is carried out by adding calcium chloride and carbon powder. When the chlorine gas is introduced, the mass ratio of the alloy particles to the chlorine gas and the carbon powder is
1:0.2 to 0.6:2 to 4, when hydrogen chloride is added or other chloride is added, the mass ratio of alloy particles to chloride to carbon powder is 1:0.2 to 0.6:2 to 4, and the baking time is 2 to
After 5 hours, the generated tail gas is absorbed by alkali solution or water spray;
（ 3 ）尾气吸收液经过多步重结晶分别回收硼酸盐与氯化盐； (3) The exhaust gas absorption liquid is separately recovered by multi-step recrystallization to recover borate and chloride salt;
（ 4 ）步骤（ 2 ）的氯化焙烧后的粉末用热稀盐酸二级逆流洗涤，溶解出可溶性的金属氯化盐，固液比
1:4 ～ 8 ，过滤得到滤液与滤渣，滤渣返回焙烧； (4) The chlorinated calcined powder of step (2) is washed with hot dilute hydrochloric acid in a two-stage countercurrent to dissolve soluble metal chloride salt, solid-liquid ratio
1:4 ～ 8 , the filtrate and the filter residue are obtained by filtration, and the filter residue is returned to roasting;
（ 5 ）将步骤（ 4 ）所得的滤液， pH 调节到 1.5 ～ 2.5
，同时通入硫化氢气体使得钴镍全部沉淀，再将溶液 pH 调节到 3.3 ～ 3.7 ，沉淀除掉铁离子；用 P507 或 P204 萃取分离 Pr 、 Nd 、
Sm 、 Dy ，再用草酸沉淀，然后对沉淀焙烧得到稀土氧化物； (5) adjusting the pH of the filtrate obtained in step (4) to 1.5 to 2.5
At the same time, hydrogen sulfide gas is introduced to precipitate all the cobalt nickel, and the pH of the solution is adjusted to 3.3 to 3.7, and the iron ions are removed by precipitation; Pr, Nd, and P517 or P204 are separated and separated.
Sm, Dy, and then precipitated with oxalic acid, and then calcined to obtain a rare earth oxide;
（ 6 ）硫化钴镍渣经过硫酸化焙烧，酸溶后，用 P507 或 P204 或 Cyanex272
萃取分离钴镍并回收钴镍。 (6) The cobalt sulfide nickel slag is calcined by sulphation, and after acid dissolution, use P507 or P204 or Cyanex272
Extraction and separation of cobalt nickel and recovery of cobalt nickel.
优选地， Preferably,
所述步骤（ 1 ）将电子废弃物永磁废料在 800 ～ 1500
℃高温下氧化熔炼成合金颗粒并磨细，磨至颗粒能够全部过 60 ～ 80 目筛。 The step (1) of the electronic waste permanent magnet waste in the 800 ~ 1500
Oxidation at high temperature °C into alloy particles and grinding, grinding to the particles can pass through 60 ~ 80 mesh sieve.
步骤（ 2 ）中合金颗粒与氯化物与碳粉的质量比为 1:0.4:3 ，焙烧时间 3 ～ 4
小时，产生的尾气用 2 ～ 10mol/l 的碱溶液喷淋吸收。In step (2), the mass ratio of the alloy particles to the chloride to the carbon powder is 1:0.4:3, and the baking time is 3 to 4
In an hour, the produced tail gas is sprayed and absorbed with an alkali solution of 2 to 10 mol/l.
所述步骤（ 4 ）中热稀盐酸是 35 ～ 65 ℃浓度为 0.1 ～ 0.3mol/l
的盐酸。 The hot dilute hydrochloric acid in the step (4) is a concentration of 0.1 to 0.3 mol/l at 35 to 65 °C.
Hydrochloric acid.
所述步骤（ 4 ）中固液比为 1:5 ～ 6 。 The solid-liquid ratio in the step (4) is 1:5 to 6.
步骤（ 5 ）沉淀除铁离子时，溶液 pH 调节到 3.4 ～ 3.6 。 Step (5) When the iron ions are precipitated, the pH of the solution is adjusted to 3.4 to 3.6.
本发明能对电子废弃物永磁材料中的稀土进行很好的回收，既可以解决电子废弃物污染问题，又提取了永磁材料中的稀土元素，实现了资源的综合利用，节约了资源。
The invention can recover the rare earth in the permanent waste material of the electronic waste well, can solve the problem of the pollution of the electronic waste, and extract the rare earth element in the permanent magnet material, realizes the comprehensive utilization of resources and saves resources.
实施例 1 Example 1
（ 1 ）将电子废弃物永磁废料在 1500 ℃高温氧化熔炼成合金颗粒并磨细，颗粒能够全部过 100
目筛。 (1) The electronic waste permanent magnet waste is oxidized and oxidized at 1500 °C into alloy particles and ground, and the particles can pass through 100.
Screen.
（ 2 ）在 1200
℃高温下通入氯气或者通入氯化氢或者加入氯化钠或者加入氯化钙，与碳粉氯化焙烧，当通入氯气时，合金颗粒与氯气与碳粉的质量比为 1:0.3:3
，当通入氯化氢或加入其它氯化物时，合金颗粒与氯化物与碳粉的质量比为 1: 0.6: 4 ，焙烧时间 2
小时。稀土、钴、镍、硼等元素几乎完全被氯化，而铁、铝、硅等几乎不被氯化，产生的尾气用 10mol/l 的碱溶液喷淋吸收。(2) at 1200
At a high temperature of °C, chlorine gas is introduced or hydrogen chloride is added or sodium chloride or calcium chloride is added, and the carbon powder is chlorinated and calcined. When chlorine gas is introduced, the mass ratio of alloy particles to chlorine gas to carbon powder is 1:0.3:3.
When the hydrogen chloride or other chloride is introduced, the mass ratio of the alloy particles to the chloride to the carbon powder is 1:0.6:4, and the baking time is 2
Hours. Elements such as rare earth, cobalt, nickel, and boron are almost completely chlorinated, while iron, aluminum, silicon, and the like are hardly chlorinated, and the generated tail gas is sprayed and absorbed with a 10 mol/l alkali solution.
（ 3 ）步骤（ 2
）中的氯化硼气体用碱溶液喷淋吸收后的溶液为硼酸盐与氯化盐的混合溶液，经过多步重结晶分别回收硼酸盐与氯化盐，硼酸盐可直接出售，氯化盐返回氯化焙烧。 (3) Steps (2)
The boron chloride gas in the alkali solution is sprayed and absorbed, and the solution is a mixed solution of borate and chloride salt. After multi-step recrystallization, the borate and the chloride salt are separately recovered, and the borate can be directly sold. The chloride salt is returned to the chlorination roasting.
（ 4 ）步骤（ 2 ）的氯化焙烧后的粉末用热稀盐酸（温度 65 ℃ , 浓度 0.1mol/l
）二级逆流洗涤，溶解出可溶性的金属氯化盐，固液比 1: 8 ，过滤得到滤液与滤渣，滤渣返回焙烧。(4) Step (2) of the chlorinated calcined powder with hot dilute hydrochloric acid (temperature 65 ° C, concentration 0.1 mol / l
The second-stage countercurrent washing dissolves the soluble metal chloride salt, and the solid-liquid ratio is 1:8. The filtrate and the filter residue are filtered, and the filter residue is returned to the roasting.
（ 5 ）步骤（ 4
）的滤液，其中含有稀土、钴、镍等的氯化物，还含有少量的铁等氯化物。将溶液的 pH 调节到 2.5
左右，同时通入硫化氢气体使得钴镍全部沉淀，而稀土离子全部留在溶液中，再将溶液 pH 调节到 3.7 ，沉淀除掉铁离子。用 P507 萃取分离 Pr 、 Nd
、 Sm 、 Dy 等，得到纯度为 99.9% 的 Pr 、 Nd 、 Sm 、 Dy 稀土盐，再用草酸沉淀焙烧得到稀土氧化物出售。 (5) Steps (4)
The filtrate contains a chloride such as rare earth, cobalt or nickel, and also contains a small amount of chloride such as iron. Adjust the pH of the solution to 2.5
At the same time, hydrogen sulfide gas is introduced at the same time to completely precipitate cobalt nickel, and the rare earth ions are all left in the solution, and the pH of the solution is adjusted to 3.7, and the iron ions are removed by precipitation. Extraction and separation of Pr and Nd with P507
, Sm, Dy, etc., obtain Pr, Nd, Sm, Dy rare earth salts with a purity of 99.9%, and then use oxalic acid precipitation roasting to obtain rare earth oxides for sale.
（ 6 ）硫化钴镍渣经过硫酸化焙烧，即在空气或者氧气氛条件下在 600 ℃焙烧 2 小时，然后用
0.5mol/l 的硫酸溶解，固液比 1:4 ，在 80 ℃反应 3 小时，用 P507 经过 12 级萃取， 10 级洗涤， 6
级反萃，得到萃余液为纯净的镍溶液和反萃液为纯净的钴溶液，再回收钴镍。(6) The cobalt sulfide nickel slag is calcined by sulfation, that is, it is baked at 600 °C for 2 hours under air or oxygen atmosphere, and then used.
Dissolve 0.5mol/l sulfuric acid, solid-liquid ratio 1:4, react at 80 °C for 3 hours, use P507 for 12-stage extraction, 10 wash, 6
The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
实施例 2Example 2
（ 1 ）将电子废弃物永磁废料 1000 ℃高温氧化熔炼成合金颗粒并磨细，颗粒能够全部过 80
目筛。 (1) The electronic waste permanent magnet waste is oxidized and oxidized at 1000 °C into alloy particles and ground, and the particles can all pass through 80
Screen.
（ 2 ）在 1000 ℃高温，通入氯气与碳粉氯化焙烧，合金颗粒与氯气与碳粉的质量比为 1:0.4:3
，焙烧时间 4 小时。稀土、钴、镍、硼等元素几乎完全被氯化，而铁、铝、硅等几乎不被氯化，产生的尾气用 8mol/l 的碱溶液喷淋吸收。 (2) At a high temperature of 1000 °C, chlorine gas and carbon powder are chlorinated, and the mass ratio of alloy particles to chlorine gas to carbon powder is 1:0.4:3.
, roasting time 4 hours. Elements such as rare earth, cobalt, nickel, and boron are almost completely chlorinated, while iron, aluminum, silicon, and the like are hardly chlorinated, and the generated tail gas is sprayed and absorbed with an alkali solution of 8 mol/l.
（ 3 ）步骤（ 2
）中的氯化硼气体用碱溶液喷淋吸收后的溶液为硼酸盐与氯化盐的混合溶液，经过多步重结晶分别回收硼酸盐与氯化盐，硼酸盐可直接出售，氯化盐返回氯化焙烧。(3) Steps (2)
The boron chloride gas in the alkali solution is sprayed and absorbed, and the solution is a mixed solution of borate and chloride salt. After multi-step recrystallization, the borate and the chloride salt are separately recovered, and the borate can be directly sold. The chloride salt is returned to the chlorination roasting.
（ 4 ）步骤（ 2 ）的氯化焙烧后的粉末用热稀盐酸（温度 50 ℃ , 浓度
0.2mol/l ）二级逆流洗涤，溶解出可溶性的金属氯化盐，固液比 1:6 ，过滤得到滤液与滤渣，滤渣返回焙烧。 (4) Step (2) of the chlorinated roasting powder with hot dilute hydrochloric acid (temperature 50 ° C, concentration
0.2mol/l) two-stage countercurrent washing, dissolving soluble metal chloride salt, solid-liquid ratio 1:6, filtering to obtain filtrate and filter residue, and returning the filter residue to roasting.
（ 5 ）步骤（ 4
）的滤液，其中含有稀土、钴、镍等的氯化物，还含有少量的铁等氯化物。将溶液的 pH 调节到 2.2
左右，同时通入硫化氢气体使得钴镍全部沉淀，而稀土离子全部留在溶液中，再将溶液 pH 调节到 3.5 左右，沉淀除掉铁离子。用 P507 萃取分离 Pr 、
Nd 、 Sm 、 Dy 等，得到纯度为 99.9% 的 Pr 、 Nd 、 Sm 、 Dy 稀土盐，再用草酸沉淀焙烧得到稀土氧化物出售。
(5) The filtrate of the step (4), which contains a chloride such as rare earth, cobalt or nickel, and further contains a small amount of chloride such as iron. The pH of the solution was adjusted to about 2.2, and hydrogen sulfide gas was introduced to precipitate all the cobalt nickel. The rare earth ions were all left in the solution, and the pH of the solution was adjusted to about 3.5, and the iron ions were removed by precipitation. Pr, Nd, Sm, Dy, etc. were extracted by P507 to obtain Pr, Nd, Sm and Dy rare earth salts with a purity of 99.9%, and then calcined with oxalic acid to obtain rare earth oxides.
（ 6 ）硫化钴镍渣经过硫酸化焙烧，即在空气或者氧气氛条件下在 600 ℃焙烧 2 小时，然后用
0.5mol/l 的硫酸溶解，固液比 1:4 ，在 80 ℃反应 3 小时，用 P507 经过 12 级萃取， 10 级洗涤， 6
级反萃，得到萃余液为纯净的镍溶液和反萃液为纯净的钴溶液，再回收钴镍。(6) The cobalt sulfide nickel slag is calcined by sulfation, that is, it is baked at 600 °C for 2 hours under air or oxygen atmosphere, and then used.
Dissolve 0.5mol/l sulfuric acid, solid-liquid ratio 1:4, react at 80 °C for 3 hours, use P507 for 12-stage extraction, 10 wash, 6
The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
实施例 3
Example 3
（ 1 ）将电子废弃物永磁废料 800 ℃高温氧化熔炼成合金颗粒并磨细，颗粒能够全部过 50
目筛。 (1) The electronic waste permanent magnet waste is oxidized and oxidized at 800 °C into alloy particles and ground, and the particles can all pass 50
Screen.
（ 2 ）在 800 ℃之间高温，通入氯气与碳粉氯化焙烧，合金颗粒与氯气与碳粉的质量比为 1:0.2:2
，焙烧时间 3 小时。稀土、钴、镍、硼等元素几乎完全被氯化，而铁、铝、硅等几乎不被氯化，产生的尾气用 2mol/l 的碱溶液喷淋吸收。(2) chlorination of chlorine gas and carbon powder at a high temperature between 800 °C, the mass ratio of alloy particles to chlorine gas to carbon powder is 1:0.2:2
The baking time is 3 hours. The elements such as rare earth, cobalt, nickel, and boron are almost completely chlorinated, while iron, aluminum, silicon, and the like are hardly chlorinated, and the generated tail gas is sprayed and absorbed by a 2 mol/l alkali solution.
（ 3 ）步骤（ 2
）中的氯化硼气体用碱溶液喷淋吸收后的溶液为硼酸盐与氯化盐的混合溶液，经过多步重结晶分别回收硼酸盐与氯化盐，硼酸盐可直接出售，氯化盐返回氯化焙烧。(3) Steps (2)
The boron chloride gas in the alkali solution is sprayed and absorbed, and the solution is a mixed solution of borate and chloride salt. After multi-step recrystallization, the borate and the chloride salt are separately recovered, and the borate can be directly sold. The chloride salt is returned to the chlorination roasting.
（ 4 ）步骤（ 2 ）的氯化焙烧后的粉末用热稀盐酸（温度 35 ℃ , 浓度
0.3mol/l ）二级逆流洗涤，溶解出可溶性的金属氯化盐，固液比 1:4 ，过滤得到滤液与滤渣，滤渣返回焙烧。 (4) Step (2) of the chlorinated roasting powder with hot dilute hydrochloric acid (temperature 35 ° C, concentration
0.3 mol/l) two-stage countercurrent washing, dissolving soluble metal chloride salt, solid-liquid ratio 1:4, filtering to obtain filtrate and filter residue, and returning the filter residue to roasting.
（ 5 ）步骤（ 4 ）的滤液，其中含有稀土、钴、镍等的氯化物，还含有少量的铁等氯化物。将溶液的 pH
调节到 1.5 ，同时通入硫化氢气体使得钴镍全部沉淀，而稀土离子全部留在溶液中，再将溶液 pH 调节到 3.3 左右，沉淀除掉铁离子。用 P204 萃取分离
Pr 、 Nd 、 Sm 、 Dy 等，得到纯度为 99.9% 的 Pr 、 Nd 、 Sm 、 Dy 稀土盐，再用草酸沉淀焙烧得到稀土氧化物出售。(5) The filtrate of the step (4), which contains a chloride such as rare earth, cobalt or nickel, and further contains a small amount of chloride such as iron. The pH of the solution
Adjusted to 1.5, while introducing hydrogen sulfide gas, the cobalt nickel is completely precipitated, and the rare earth ions are all left in the solution, and then the pH of the solution is adjusted to about 3.3, and the iron ions are precipitated and removed. Extraction separation with P204
Pr, Nd, Sm, Dy, etc., get Pr, Nd, Sm, Dy rare earth salts with a purity of 99.9%, and then calcined with oxalic acid to obtain rare earth oxides for sale.
（ 6 ）硫化钴镍渣经过硫酸化焙烧，在 600 ℃焙烧 2 小时，然后用 0.5mol/l
的硫酸溶解，固液比 1:4 ，在 80 ℃反应 3 小时，用 P204 经过 12 级萃取， 10 级洗涤， 6
级反萃，得到萃余液为纯净的镍溶液和反萃液为纯净的钴溶液，再回收钴镍。 (6) The cobalt sulfide nickel slag is calcined by sulfation, calcined at 600 °C for 2 hours, and then 0.5 mol/l
The sulfuric acid is dissolved, the solid-liquid ratio is 1:4, the reaction is carried out at 80 °C for 3 hours, and the P204 is subjected to 12-stage extraction, 10 stages of washing, 6
The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
实施例 4 Example 4
（ 1 ）将电子废弃物永磁废料 1200 ℃高温氧化熔炼成合金颗粒并磨细，颗粒能够全部过 70
目筛。 (1) The electronic waste permanent magnet waste is oxidized at 1200 °C to form alloy particles and ground, and the particles can pass through 70.
Screen.
（ 2 ）在 1100 ℃高温，通入氯气与碳粉氯化焙烧，合金颗粒与氯气与碳粉的质量比为
1:0.5:2.8 ，焙烧时间 5 小时。稀土、钴、镍、硼等元素几乎完全被氯化，而铁、铝、硅等几乎不被氯化，产生的尾气用水喷淋吸收。(2) At a high temperature of 1100 °C, chlorine gas and carbon powder are chlorinated, and the mass ratio of alloy particles to chlorine gas and carbon powder is
1:0.5:2.8, baking time 5 hours. Elements such as rare earth, cobalt, nickel, and boron are almost completely chlorinated, while iron, aluminum, silicon, and the like are hardly chlorinated, and the generated tail gas is sprayed and absorbed by water.
（ 3 ）步骤（ 2
）中的氯化硼气体用水喷淋吸收后的溶液为硼酸盐与溶液，经过多步重结晶分别回收硼酸盐与氯化盐，硼酸盐可直接出售，氯化盐返回氯化焙烧。(3) Steps (2)
The boron chloride gas in the water is sprayed and absorbed, and the solution is borate and solution. After multi-step recrystallization, the borate and the chloride salt are separately recovered. The borate can be directly sold, and the chloride salt is returned to the chlorination roasting. .
（ 4 ）步骤（ 2 ）的氯化焙烧后的粉末用热稀盐酸（温度 45 ℃ , 浓度
0.2mol/l ）二级逆流洗涤，溶解出可溶性的金属氯化盐，固液比 1:5 ，过滤得到滤液与滤渣，滤渣返回焙烧。 (4) Step (2) of the chlorinated roasting powder with hot dilute hydrochloric acid (temperature 45 ° C, concentration
0.2mol/l) secondary countercurrent washing, dissolving soluble metal chloride salt, solid-liquid ratio 1:5, filtering to obtain filtrate and filter residue, and returning the filter residue to roasting.
（ 5 ）步骤（ 4 ）的滤液，其中含有稀土、钴、镍等的氯化物，还含有少量的铁等氯化物。将溶液的 pH
调节到 2.5 ，同时通入硫化氢气体使得钴镍全部沉淀，而稀土离子全部留在溶液中，再将溶液 pH 调节到 3.7 ，沉淀除掉铁离子。用 P507 萃取分离 Pr
、 Nd 、 Sm 、 Dy 等，得到纯度为 99.9% 的 Pr 、 Nd 、 Sm 、 Dy 稀土盐，再用草酸沉淀焙烧得到稀土氧化物出售。(5) The filtrate of the step (4), which contains a chloride such as rare earth, cobalt or nickel, and further contains a small amount of chloride such as iron. The pH of the solution
Adjusted to 2.5, while introducing hydrogen sulfide gas, the cobalt nickel is completely precipitated, and the rare earth ions are all left in the solution, and then the pH of the solution is adjusted to 3.7, and the iron ions are removed by precipitation. Extraction separation with P507 Pr
, Nd, Sm, Dy, etc., get Pr, Nd, Sm, Dy rare earth salts with a purity of 99.9%, and then roast with oxalic acid to obtain rare earth oxides for sale.
（ 6 ）硫化钴镍渣经过硫酸化焙烧，即在空气或者氧气氛下在 600 ℃焙烧 2
小时，然后用 0.5mol/l 的硫酸溶解，固液比 1:4 ，在 80 ℃反应 3 小时，用 P507 经过 12 级萃取， 10 级洗涤， 6
级反萃，得到萃余液为纯净的镍溶液和反萃液为纯净的钴溶液，再回收钴镍。 (6) The cobalt sulfide nickel slag is calcined by sulphation, that is, calcined at 600 ° C under air or oxygen atmosphere 2
Hour, then dissolve with 0.5mol/l sulfuric acid, solid-liquid ratio 1:4, react at 80 °C for 3 hours, use P507 for 12-stage extraction, 10 wash, 6
The stage is stripped, and the raffinate is obtained as a pure nickel solution and the stripping solution is a pure cobalt solution, and then cobalt nickel is recovered.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and combinations thereof may be made without departing from the spirit and scope of the invention. Simplifications should all be equivalent replacements and are included in the scope of the present invention.
Claims (6)
- 一种电子废弃物永磁废料中回收稀土的工艺，其特征是，包括以下步骤：A process for recovering rare earth in an electronic waste permanent magnet waste, characterized in that the method comprises the following steps:（ 1 ）将电子废弃物永磁废料高温氧化熔炼成合金颗粒并磨细，磨至颗粒能够全部过 50 ～ 100 目筛；(1) High-temperature oxidation of permanent waste of electronic waste into alloy particles and grinding, grinding to particles can pass 50 ~ 100 Mesh sieve（ 2 ）在 800 ～ 1200 ℃条件下，通入氯气并加入碳粉氯化焙烧；或者通入氯化氢并加入碳粉氯化焙烧；或者加入氯化钠和碳粉氯化焙烧；或者加入氯化钙和碳粉氯化焙烧；当通入氯气时，合金颗粒与氯气与碳粉的质量比为 1:0.2 ～ 0.6:2 ～ 4 ，当通入氯化氢或加入其它氯化物时，合金颗粒与氯化物与碳粉的质量比为 1:0.2 ～ 0.6:2 ～ 4 ；焙烧时间 2 ～ 5 小时，产生的尾气采用碱溶液或水喷淋吸收；(2) at 800 to 1200 Under the condition of °C, chlorine gas is introduced and chlorinated by adding carbon powder; or hydrogen chloride is added and chlorinated by adding carbon powder; or chlorination is carried out by adding sodium chloride and carbon powder; or chlorination is carried out by adding calcium chloride and carbon powder. When the chlorine gas is introduced, the mass ratio of the alloy particles to the chlorine gas and the carbon powder is 1:0.2 to 0.6:2 to 4, when hydrogen chloride is added or other chloride is added, the mass ratio of alloy particles to chloride to carbon powder is 1:0.2 to 0.6:2 to 4; roasting time 2 to After 5 hours, the generated tail gas is absorbed by alkali solution or water spray;（ 3 ）尾气吸收液经过多步重结晶分别回收硼酸盐与氯化盐；(3) The exhaust gas absorption liquid is separately recovered by multi-step recrystallization to recover borate and chloride salt;（ 4 ）步骤（ 2 ）的氯化焙烧后的粉末用热稀盐酸二级逆流洗涤，溶解出可溶性的金属氯化盐，固液比 1:4 ～ 8 ，过滤得到滤液与滤渣，滤渣返回焙烧；(4) The chlorinated calcined powder of step (2) is washed with hot dilute hydrochloric acid in a two-stage countercurrent to dissolve soluble metal chloride salt, and the solid-liquid ratio is 1:4-8 Filtering to obtain filtrate and filter residue, and returning the filter residue to roasting;（ 5 ）将步骤（ 4 ）所得的滤液， pH 调节到 1.5 ～ 2.5 ，同时通入硫化氢气体使得钴镍全部沉淀，再将溶液 pH 调节到 3.3 ～ 3.7 ，沉淀除掉铁离子；用 P507 或 P204 萃取分离 Pr 、 Nd 、 Sm 、 Dy ，再用草酸沉淀焙烧得到稀土氧化物；(5) adjusting the pH of the filtrate obtained in the step (4) to 1.5 to 2.5, and simultaneously introducing hydrogen sulfide gas to precipitate all the cobalt nickel, and then the solution The pH is adjusted to 3.3 ~ 3.7, the iron ions are removed by precipitation, and Pr, Nd, Sm, Dy are separated by P507 or P204. And then calcined with oxalic acid to obtain a rare earth oxide;（ 6 ）硫化钴镍渣经过硫酸化焙烧，酸溶后，用 P507 或 P204 或 Cyanex272 萃取分离钴镍并回收钴镍。(6) The cobalt sulfide nickel slag is calcined by sulphation, and after acid dissolution, use P507 or P204 or Cyanex272 Extraction and separation of cobalt nickel and recovery of cobalt nickel.
- 根据权利要求 1 所述的电子废弃物永磁废料中回收稀土的工艺，其特征是，所述步骤（ 1 ）将电子废弃物永磁废料在 800 ～ 1500 ℃高温下氧化熔炼成合金颗粒并磨细，磨至颗粒能够全部过 60 ～ 80 目筛。The process for recovering rare earth in an electronic waste permanent magnet waste according to claim 1, wherein the step (1) of the electronic waste permanent magnet waste is 800 ~ 1500 °C high temperature oxidation smelting into alloy particles and grinding, grinding until the particles can pass through 60 ~ 80 mesh sieve.
- 根据权利要求 1 所述的电子废弃物永磁废料中回收稀土的工艺，其特征是，步骤（ 2 ）中合金颗粒与氯化物与碳粉的质量比为 1:0.4:3 ，焙烧时间 3 ～ 4 小时，产生的尾气用 2 ～ 10mol/l 的碱溶液喷淋吸收。The process for recovering rare earth in the permanent waste of electronic waste according to claim 1, wherein the mass ratio of the alloy particles to the chloride to the carbon powder in the step (2) is 1:0.4:3, the calcination time is 3 to 4 hours, and the generated tail gas is sprayed and absorbed with 2 to 10 mol/l of an alkali solution.
- 根据权利要求 1 所述的电子废弃物永磁废料中回收稀土的工艺，其特征是，所述步骤（ 4 ）中热稀盐酸是 35 ～ 65 ℃浓度为 0.1 ～ 0.3mol/l 的盐酸。The process for recovering rare earth in the permanent waste of electronic waste according to claim 1, wherein the hot dilute hydrochloric acid in the step (4) is 35 to 65 The concentration of °C is 0.1 to 0.3 mol/l of hydrochloric acid.
- 根据权利要求 1 所述的电子废弃物永磁废料中回收稀土的工艺，其特征是，所述步骤（ 4 ）中固液比为 1:5 ～ 6 。The process for recovering rare earth in the permanent waste of electronic waste according to claim 1, wherein the solid-liquid ratio in the step (4) is 1:5 to 6 .
- 根据权利要求 1 所述的电子废弃物永磁废料中回收稀土的工艺，其特征是，步骤（ 5 ）沉淀除铁离子时，溶液 pH 调节到 3.4 ～ 3.6 。The process for recovering rare earth in the permanent waste of electronic waste according to claim 1, wherein in step (5), when the iron ion is precipitated, the pH of the solution is adjusted to 3.4 ~ 3.6.
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| CN201210216652.XA CN103509952B (en) | 2012-06-28 | 2012-06-28 | The technique of recovering rare earth in a kind of electron wastes permanent magnet spent material |
| CN201210216652.X | 2012-06-28 |
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| PCT/CN2012/087752 WO2014000404A1 (en) | 2012-06-28 | 2012-12-28 | Process for recycling rare earths in permanent magnet scrap of electronic waste |
Country Status (2)
| Country | Link |
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| CN (1) | CN103509952B (en) |
| WO (1) | WO2014000404A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110044999A (en) * | 2019-05-06 | 2019-07-23 | 中国工程物理研究院化工材料研究所 | The detection method of 14 kinds of trace impurity rare earth ion contents in a kind of ultra-pure cerium compound |
| WO2020151478A1 (en) * | 2019-01-21 | 2020-07-30 | 中国科学院金属研究所 | Method for recovering rare earth element from neodymium-iron-boron scrap by means of extraction with liquid metal bismuth |
| CN112609076A (en) * | 2020-11-27 | 2021-04-06 | 中国科学院长春应用化学研究所 | Method for recovering rare earth oxide from waste rare earth polishing powder |
| CN113667822A (en) * | 2021-07-15 | 2021-11-19 | 江西理工大学 | Method for recovering neodymium iron boron waste through magnesium roasting |
| CN115418505A (en) * | 2022-08-25 | 2022-12-02 | 萍乡泽昊新材料有限责任公司 | Method for removing cerium and non-rare earth impurities from rare earth feed liquid |
| CN116043016A (en) * | 2022-07-19 | 2023-05-02 | 江苏南方永磁科技有限公司 | Preparation method and application of neodymium oxide |
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| EP3715482A1 (en) | 2019-03-29 | 2020-09-30 | Tata Consultancy Services Limited | Method and system for separation of rare earth elements from secondary sources |
| CN112853107A (en) * | 2021-01-19 | 2021-05-28 | 连云港高品再生资源有限公司 | Method for treating rare earth permanent magnet waste |
| CN115505742B (en) * | 2022-10-12 | 2024-07-09 | 中国恩菲工程技术有限公司 | Samarium cobalt recovery method of samarium cobalt magnetic material |
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| CN102011020A (en) * | 2009-12-14 | 2011-04-13 | 包头市玺骏稀土有限责任公司 | Method for recovering rare earth elements from neodymium-iron-boron wastes |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020151478A1 (en) * | 2019-01-21 | 2020-07-30 | 中国科学院金属研究所 | Method for recovering rare earth element from neodymium-iron-boron scrap by means of extraction with liquid metal bismuth |
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| CN112609076A (en) * | 2020-11-27 | 2021-04-06 | 中国科学院长春应用化学研究所 | Method for recovering rare earth oxide from waste rare earth polishing powder |
| CN113667822A (en) * | 2021-07-15 | 2021-11-19 | 江西理工大学 | Method for recovering neodymium iron boron waste through magnesium roasting |
| CN116043016A (en) * | 2022-07-19 | 2023-05-02 | 江苏南方永磁科技有限公司 | Preparation method and application of neodymium oxide |
| CN115418505A (en) * | 2022-08-25 | 2022-12-02 | 萍乡泽昊新材料有限责任公司 | Method for removing cerium and non-rare earth impurities from rare earth feed liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103509952A (en) | 2014-01-15 |
| CN103509952B (en) | 2015-12-09 |
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