CN113621804A - Method for separating and recycling rare earth and iron from neodymium iron boron waste - Google Patents
Method for separating and recycling rare earth and iron from neodymium iron boron waste Download PDFInfo
- Publication number
- CN113621804A CN113621804A CN202110798810.6A CN202110798810A CN113621804A CN 113621804 A CN113621804 A CN 113621804A CN 202110798810 A CN202110798810 A CN 202110798810A CN 113621804 A CN113621804 A CN 113621804A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- iron boron
- neodymium iron
- ferrate
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 88
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 76
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 74
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 32
- 230000001590 oxidative effect Effects 0.000 claims abstract description 30
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 35
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 33
- 239000011734 sodium Substances 0.000 claims description 33
- 229910052708 sodium Inorganic materials 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 26
- 238000000926 separation method Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 rare earth chloride Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of neodymium iron boron waste recovery, in particular to a method for separating and recovering rare earth and iron from neodymium iron boron waste; in the invention, an additive is adopted to react with ferric oxide in the neodymium iron boron calcine under the high temperature condition to generate ferrate dissolved in water, then water is adopted to leach out, the ferrate dissolved in water is dissolved out to obtain leachate, and the oxidized rare earth is insoluble in water and still belongs to a solid state, so that the purposes of efficient recovery of rare earth and selective separation of rare earth and iron are realized, then the ferrate in the leachate is oxidized by an oxidant to generate ferrate, and then potassium hydroxide is adopted to react with the ferrate to form crystals, and then the crystals are filtered, so that the potassium ferrate with high added value is obtained, and the purpose of recovering iron is achieved; the method has the advantages of low cost, good separation effect of the rare earth and the iron, high recovery rate of the rare earth and the iron and high comprehensive utilization rate of resources.
Description
Technical Field
The invention relates to the technical field of neodymium iron boron waste recovery, in particular to a method for separating and recovering rare earth and iron from neodymium iron boron waste.
Background
Neodymium iron boron is an excellent permanent magnet, which yields over 20 million tons in 2020 and increases at a rate of 10% per year. With the increasing demand of neodymium iron boron and the expiration of product life, more and more neodymium iron boron is discarded, and the neodymium iron boron waste material refers to solid waste materials such as invalid neodymium iron boron magnet or oil sludge and leftover materials generated in the grinding, grinding and cutting processes of neodymium iron boron magnet.
In the process of grinding, cutting and cutting the neodymium iron boron magnet, about 30% of neodymium iron boron waste materials are generated when one ton of neodymium iron boron magnet is produced, and the waste materials have high value due to the fact that the waste materials contain 20-30% of rare earth and 60-70% of iron, so that the important significance of recycling valuable metals such as rare earth, iron and the like from the neodymium iron boron waste materials is achieved.
At present, the rare earth is mainly recovered from the neodymium iron boron waste in China, for example, the rare earth in the neodymium iron boron waste is recovered by adopting a roasting-hydrochloric acid leaching process, although the leaching rate of the rare earth is high, iron and iron-rich slag in a liquid obtained after the recovery of the rare earth are not further treated and recovered, and the adoption of acid leaching not only corrodes equipment, but also generates a large amount of chlorine-containing wastewater. Most students pay attention to the selective separation and recovery of rare earth with high value in the recovery process of neodymium iron boron waste, but have fresh research on iron resources with the largest proportion, so that a large amount of iron slag or iron-containing wastewater is generated, and direct stacking or discharging not only wastes iron resources, but also pollutes the environment.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a method for separating and recovering rare earth and iron from neodymium iron boron waste, which adopts an additive to react with iron oxide in neodymium iron boron calcine under a high temperature condition to generate water-soluble ferrite, then adopts water leaching to dissolve out the water-soluble ferrite to obtain a leaching solution, the rare earth oxide is insoluble in water and still belongs to a solid state, thereby realizing the purposes of efficient recovery of the rare earth and selective separation of the rare earth and the iron, then adopts an oxidant to oxidize the ferrite in the leaching solution to generate ferrate, and then adopts potassium hydroxide to react with the ferrate to form crystals and then filter, thereby obtaining the potassium ferrate with high added value and achieving the purpose of recovering the iron.
The technical scheme for solving the technical problem is as follows:
a method for separating and recovering rare earth and iron from neodymium iron boron waste materials comprises the following steps:
s1, uniformly mixing the neodymium iron boron waste with the additive, and roasting to obtain neodymium iron boron roasted sand;
s2, mixing the neodymium iron boron calcine with water, leaching, and filtering to obtain leachate and rare earth oxide;
s3, mixing the leachate with an oxidant, and stirring to obtain a sodium ferrate mixed solution;
s4, mixing the mixed solution of sodium ferrate and potassium hydroxide solution, stirring uniformly, crystallizing and filtering to obtain potassium ferrate and a solution after iron precipitation.
As an improvement of the invention, in step S1, the neodymium iron boron waste and the additive are uniformly mixed according to the mass ratio of 1 (2-5).
As a further improvement of the invention, in step S1, the neodymium iron boron waste is mixed with the additive and then roasted for 2-6 h at 600-1200 ℃, so as to obtain the neodymium iron boron roasted sand.
As a further improvement of the invention, the additive comprises at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium oxide.
As a further improvement of the invention, the additive comprises at least one of potassium carbonate, potassium bicarbonate, potassium hydroxide and potassium oxide.
As a further improvement of the invention, in step S2, the neodymium iron boron calcine is mixed with water according to the mass-to-volume ratio of 1 (3-8).
As a further improvement of the invention, in step S2, the neodymium iron boron calcine is mixed with water, leached for 0.5 to 4 hours at 60 to 90 ℃, and then filtered, so as to obtain a leaching solution and rare earth oxide.
In a further improvement of the present invention, in step S3, the leachate and the oxidizing agent are mixed in a molar ratio of ferric iron to the oxidizing agent of 1: (2-6).
As a further improvement of the invention, in step S3, the leachate is mixed with the oxidant and then stirred for 1-4 hours at 60-90 ℃ to obtain a sodium ferrate mixed solution.
In a further improvement of the present invention, in step S4, the sodium ferrate mixed solution and the potassium hydroxide solution are mixed according to a volume ratio of 1 (1-2) to the potassium hydroxide solution.
In the invention, an additive is adopted to react with ferric oxide in the neodymium iron boron calcine under the high temperature condition to generate ferrate dissolved in water, then water is adopted to leach out, the ferrate dissolved in water is dissolved out to obtain leachate, and the oxidized rare earth is insoluble in water and still belongs to a solid state, so that the purposes of efficient recovery of rare earth and selective separation of rare earth and iron are realized, then the ferrate in the leachate is oxidized by an oxidant to generate ferrate, and then potassium hydroxide is adopted to react with the ferrate to form crystals, and then the crystals are filtered, so that the potassium ferrate with high added value is obtained, and the purpose of recovering iron is achieved.
Drawings
For ease of illustration, the present invention is described in detail by the following preferred embodiments and the accompanying drawings.
FIG. 1 is a block diagram of the present invention;
FIG. 2 is a process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, a plurality of scholars in China research the recovery of rare earth in neodymium iron boron waste materials, for example, Denghua army (Denghua army, Duyuhong, Dengheng Phoenix, recovery of rare earth in neodymium iron boron waste materials [ J ]. mining and metallurgy engineering, 2019, 39 (1): 76-78) adopt roasting-hydrochloric acid leaching process to recover rare earth in neodymium iron boron waste materials, and experimental results show that the optimal roasting conditions of the neodymium iron boron waste materials are as follows: the roasting temperature is 700 ℃, the roasting time is 1.5h, and the iron oxidation rate can reach 99.30 percent; the best condition for leaching the roasted material by hydrochloric acid is as follows: the hydrochloric acid concentration is 4mol/L, and the liquid-solid ratio is 3: 1. the leaching temperature is 90 ℃, the leaching time is 1.5h, the leaching rate of the rare earth can reach 98.11%, although the leaching rate of the rare earth is high, the iron and the iron-rich slag in the rare earth recovery liquid are not further treated and recovered, and the acid leaching is adopted, so that the equipment is corroded, and a large amount of chlorine-containing wastewater is generated.
For another example, Liu Qing Sheng (Liu Qing Sheng, Lu Ying Wei, segmented Xue, Nd-Fe-B waste (NH4)2SO4Recovery of rare-earth by roasting method]Chinese rare earth journal, 2019, 37 (1): 91-98) mixing the neodymium iron boron waste with (NH4)2SO4, roasting, and selectively recovering rare earth in the neodymium iron boron waste, wherein the results show that: roasting at 400 deg.C for 120 min, and mixing neodymium iron boron with (NH4)2SO4The mass ratio of the mixed materials is 1: 2, the leaching rate of the rare earth can be higher under the condition, the leaching rate is about 92 percent, the leaching rate of the Fe is only 3 percent, although the selective separation of the rare earth and the iron is realized by the process, the leaching rate of the rare earth is low, and the iron-rich leaching slag is not further treated and recovered.
For another example, in the "method for recovering rare earth from neodymium iron boron waste by high-temperature high-pressure leaching" (CN 109554549A) ", firstly, the neodymium iron boron waste is oxidized and roasted at 800 ℃, then the neodymium iron boron waste is leached by hydrochloric acid at high temperature and high pressure to obtain leachate, and then Fe in the leachate is added2+The rare earth chloride leaching solution is obtained through oxidation and impurity removal purification, rare earth is obtained through extraction and separation of the leaching solution, rare earth carbonate is prepared through precipitation, or rare earth oxide is prepared through precipitation roasting, although the rare earth is better recovered through the process, the process is harsh in conditions of high temperature and high pressure, high in equipment requirement, and hydrochloric acid has volatility, is easy to leak, causes environmental pollution, and generates a large amount of chlorine-containing wastewater.
The invention improves the recovery of rare earth and iron in neodymium iron boron waste, and recovers the iron while recovering the rare earth.
As shown in fig. 1 and 2, the method for separating and recovering rare earth and iron from neodymium iron boron waste comprises the following steps:
s1, uniformly mixing the neodymium iron boron waste with the additive, and roasting to obtain neodymium iron boron roasted sand;
s2, mixing the neodymium iron boron calcine with water, leaching, and filtering to obtain leachate and rare earth oxide;
s3, mixing the leachate with an oxidant, and stirring to obtain a sodium ferrate mixed solution;
s4, mixing the mixed solution of sodium ferrate and potassium hydroxide solution, stirring uniformly, crystallizing and filtering to obtain potassium ferrate and a solution after iron precipitation.
In the invention, an additive is adopted to react with ferric oxide in the neodymium iron boron calcine under the high temperature condition to generate ferrate dissolved in water, then water is adopted to leach out, the ferrate dissolved in water is dissolved out to obtain leachate, and the oxidized rare earth is insoluble in water and still belongs to a solid state, so that the purposes of efficient recovery of rare earth and selective separation of rare earth and iron are realized, then the ferrate in the leachate is oxidized by an oxidant to generate ferrate, and then potassium hydroxide is adopted to react with the ferrate to form crystals, and then the crystals are filtered, so that the potassium ferrate with high added value is obtained, and the purpose of recovering iron is achieved.
In the invention, in step S1, uniformly mixing neodymium iron boron waste with an additive according to a mass ratio of 1 (2-5), and roasting at 600-1200 ℃ for 2-6 h to obtain neodymium iron boron calcine; the additive comprises at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium oxide, or the additive comprises at least one of potassium carbonate, potassium bicarbonate, potassium hydroxide and potassium oxide, if the additive comprises at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium oxide, the neodymium iron boron waste and the additive are uniformly mixed, and then roasting is carried out, so as to obtain sodium ferrite; if the additive comprises at least one of potassium carbonate, potassium bicarbonate, potassium hydroxide and potassium oxide, uniformly mixing the neodymium-iron-boron waste material and the additive, and roasting to obtain potassium ferrite, wherein the sodium ferrite and the potassium ferrite are both dissolved in water. In step S1, the additive is not too much and not too little, and if too much, the additive is wasted, the cost is increased, and if too little, the iron in the neodymium iron boron waste material cannot be separated.
In the step 1, the roasting temperature is 600-1200 ℃, which cannot be too low, because the temperature is lower than 600 ℃, the reaction is insufficient, and if the temperature is too high, redundant impurities exist.
In the invention, in step S2, according to the mass to volume ratio of 1 (3-8), mixing the neodymium iron boron calcine with water, leaching for 0.5-4 h at 60-90 ℃, and filtering to obtain leachate and rare earth oxide; the rare earth oxide can be dissolved by acid and then a single rare earth product is obtained by adopting a solvent extraction method, or a single rare earth metal is prepared by adopting a molten salt electrolysis method, so that the recovery of the rare earth is achieved; leaching the rare earth oxide by a water leaching method, wherein the leaching time is 0.5-4 h, which cannot be less than half an hour, or else, the leaching is incomplete, leaching is carried out for 4 hours at 60 ℃, and the rare earth oxide can be well leached under the condition that the neodymium iron boron calcine and water are mixed according to the mass-volume ratio of 1 (3-8).
In step S3, mixing a leaching solution with an oxidant according to a molar ratio of ferric iron to the oxidant of 1: 2-6, stirring for 1-4 h at 60-90 ℃ to obtain a sodium ferrate mixed solution, wherein the oxidant comprises at least one of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, the strong oxidant is adopted to react with the sodium ferrate to generate the sodium ferrate mixed solution, and the leaching solution is mixed with the oxidant, so that the molar ratio of ferric iron to the oxidant is 1: 2-6, the oxidation reaction can be better performed, the oxidant is excessive, if the oxidant is too high, the oxidation is incomplete, the stirring and the oxidation are required to be performed for 1h at least, and the stirring is performed for 4h at 60 ℃ to better perform the complete reaction and oxidation.
In step S4, according to the volume ratio of the sodium ferrate mixed solution to the potassium hydroxide solution being 1 (1-2), mixing the sodium ferrate mixed solution with the potassium hydroxide solution, stirring uniformly, crystallizing at 0-5 ℃, filtering, and then washing for 2-3 times with the potassium hydroxide solution to obtain potassium ferrate and a solution after iron precipitation, wherein the concentration of the potassium hydroxide solution is 40-60 wt%; specifically, a potassium hydroxide solution with the concentration of 40-60 wt% is reacted with a sodium ferrate mixed solution, the ratio of the potassium hydroxide solution to the sodium ferrate mixed solution is 1 (1-2), the potassium hydroxide solution is not easy to be excessive, otherwise, the potassium hydroxide solution is wasted, and the replacement is insufficient; the mixed solution of sodium ferrate and potassium hydroxide solution are mixed, stirred uniformly and crystallized at the temperature of 0-5 ℃, otherwise, the temperature cannot exceed 5 ℃, and finally the potassium ferrate and the solution after iron precipitation can be obtained by washing with the potassium hydroxide solution for 2-3 times, wherein the potassium ferrate is an excellent oxidant, has an efficient disinfection effect, is a novel non-chlorine efficient disinfectant, is mainly used for drinking water treatment, is used as an oxidant of sulfonic acid, nitrite, ferrocyanide and other inorganic substances in chemical production, is used for removing manganese, antimony and arsenic in zinc smelting, and is used for cigarette filters in the tobacco industry.
For a better illustration and explanation of the invention, several examples are given below:
to avoid repetition, the chemical compositions of the neodymium iron boron waste materials in the examples are as follows: 5-15% of Nd, 5-15% of Ce, 1-5% of Pr, 1-5% of Gd, 1-5% of Dy, 0.5-3% of Sm and 40-70% of Fe.
The first embodiment is as follows:
(1) uniformly mixing the neodymium iron boron waste with sodium carbonate according to the mass ratio of 1: 2, and roasting for 6 hours at the temperature of 800 ℃ to obtain neodymium iron boron calcine;
(2) mixing the neodymium iron boron calcine with water according to the mass-to-volume ratio of 1: 3, stirring for 4 hours at the temperature of 60 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leaching solution with an oxidant according to the molar ratio of ferric iron to the oxidant of 1: 2, and stirring for 3 hours at the temperature of 60 ℃ to obtain a sodium ferrate mixed solution;
(4) mixing the mixed solution of sodium ferrate and potassium hydroxide solution according to the volume ratio of 1: 1, uniformly stirring, crystallizing at 0 ℃, filtering, washing for 3 times by using potassium hydroxide solution to obtain potassium ferrate and a solution after iron precipitation; the concentration of the potassium hydroxide solution was 40 wt%.
The results obtained in this example one are as follows: the leaching rate of iron is 98.85 percent, and the leaching rate of rare earth is 0.26 percent; the total recovery rate of iron is 96.54 percent, and the total recovery rate of rare earth is 97.42 percent; the purity of the potassium ferrate is 99.23 percent.
Example two:
(1) uniformly mixing neodymium iron boron waste with sodium hydroxide according to the mass ratio of 1: 3, and roasting at 900 ℃ for 4 hours to obtain neodymium iron boron calcine;
(2) mixing the neodymium iron boron calcine with water according to the mass-to-volume ratio of 1: 4, stirring for 2 hours at 90 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leaching solution with an oxidant according to the molar ratio of ferric iron to the oxidant of 1: 3, and stirring for 3.5 hours at the temperature of 90 ℃ to obtain a sodium ferrate mixed solution;
(4) mixing the mixed solution of sodium ferrate and potassium hydroxide solution according to the volume ratio of 1: 1.2, uniformly stirring, crystallizing at 5 ℃, filtering, washing for 3 times by using potassium hydroxide solution to obtain potassium ferrate and a solution after iron precipitation; the concentration of the potassium hydroxide solution was 45 wt%.
The results obtained in example two are as follows: the leaching rate of iron is 99.04 percent, and the leaching rate of rare earth is 0.35 percent; the total recovery rate of iron is 97.16 percent, and the total recovery rate of rare earth is 98.13 percent; the purity of the potassium ferrate is 99.42 percent.
Example three:
(1) uniformly mixing neodymium iron boron waste with sodium bicarbonate according to the mass ratio of 1: 4, and roasting at 1000 ℃ for 3 hours to obtain neodymium iron boron calcine;
(2) mixing the neodymium iron boron calcine with water according to the mass-to-volume ratio of 1: 5, stirring for 4 hours at the temperature of 60 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leaching solution with an oxidant according to the molar ratio of ferric iron to the oxidant of 1: 4, and stirring for 4 hours at the temperature of 60 ℃ to obtain a sodium ferrate mixed solution;
(4) mixing the mixed solution of sodium ferrate and potassium hydroxide solution according to the volume ratio of 1: 1.5, uniformly stirring, crystallizing at 0 ℃, filtering, washing for 3 times by using potassium hydroxide solution to obtain potassium ferrate and a solution after iron precipitation; the concentration of the potassium hydroxide solution is 50 wt%.
The results obtained in example three are as follows: the leaching rate of iron is 98.47 percent, and the leaching rate of rare earth is 0.57 percent; the total recovery rate of iron is 96.72 percent, and the total recovery rate of rare earth is 98.28 percent; the purity of the potassium ferrate is 99.20%.
Example four:
(1) uniformly mixing neodymium iron boron waste with potassium carbonate according to the mass ratio of 1: 3, and roasting at 600 ℃ for 4 hours to obtain neodymium iron boron roasted sand;
(2) mixing the neodymium iron boron calcine with water according to the mass-to-volume ratio of 1: 7, stirring for 2 hours at 90 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leaching solution with an oxidant according to the molar ratio of ferric iron to the oxidant of 1: 5, and stirring for 3.5 hours at the temperature of 90 ℃ to obtain a potassium ferrate solution;
(4) mixing the mixed solution of sodium ferrate and potassium hydroxide solution according to the volume ratio of 1: 2, uniformly stirring, crystallizing at 5 ℃, filtering, washing for 3 times by using potassium hydroxide solution to obtain potassium ferrate and a solution after iron precipitation; the concentration of the potassium hydroxide solution was 55 wt%.
The results obtained for the fourth example are as follows: the leaching rate of iron is 99.06 percent, and the leaching rate of rare earth is 0.30 percent; the total recovery rate of iron is 97.20 percent, and the total recovery rate of rare earth is 98.08 percent; the purity of the potassium ferrate is 99.46%.
The results of examples one to four are compared as follows:
the invention has the following advantages:
1. in the invention, the additive is adopted to react with ferric oxide at high temperature to generate sodium ferrite (or potassium ferrite) dissolved in water, then the sodium ferrite (or potassium ferrite) dissolved in water is leached out by adopting water, and the rare earth oxide is not dissolved in water and still remains in slag, thereby realizing the selective separation of rare earth and iron.
The invention adopts strong oxidant to oxidize sodium ferrite in the leaching solution to be sodium ferrate (or potassium ferrate), then adopts potassium hydroxide to replace sodium, and further crystallizes to obtain high value-added product potassium ferrate, and the iron is comprehensively recycled, thereby having the characteristic of high comprehensive utilization rate of resources.
The method adopts a sodium (potassium) roasting-water leaching process to realize the selective separation of the rare earth and the iron in the neodymium iron boron waste, the leaching rate of the iron is more than 98 percent, the leaching rate of the rare earth is lower than 1 percent, and the oxidized rare earth can be dissolved by acid and then is subjected to a solvent extraction method to obtain a single rare earth product or a single rare earth metal is prepared by a molten salt electrolysis method; the potassium ferrate is obtained from the iron-rich leaching solution by an oxidation-crystallization method, and the purity of the potassium ferrate is more than 99 percent; the total recovery rate of the rare earth and the iron is more than 96 percent.
Therefore, the method has the characteristics of low cost, good rare earth and iron separation effect, high rare earth and iron recovery rate and high comprehensive resource utilization rate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for separating and recycling rare earth and iron from neodymium iron boron waste is characterized by comprising the following steps:
s1, uniformly mixing the neodymium iron boron waste with the additive, and roasting to obtain neodymium iron boron roasted sand;
s2, mixing the neodymium iron boron calcine with water, leaching, and filtering to obtain leachate and rare earth oxide;
s3, mixing the leachate with an oxidant, and stirring to obtain a sodium ferrate mixed solution;
s4, mixing the mixed solution of sodium ferrate and potassium hydroxide solution, stirring uniformly, crystallizing and filtering to obtain potassium ferrate and a solution after iron precipitation.
2. The method for separating and recovering rare earth and iron from neodymium iron boron waste according to claim 1, wherein in step S1, the neodymium iron boron waste and an additive are uniformly mixed according to a mass ratio of 1 (2-5).
3. The method for separating and recycling rare earth and iron from neodymium iron boron waste according to claim 2, characterized in that in step S1, the neodymium iron boron waste is mixed with an additive and then roasted for 2-6 h at 600-1200 ℃, so as to obtain neodymium iron boron calcine.
4. The method for separating and recovering rare earth and iron from neodymium iron boron waste according to claim 3, wherein the additive comprises at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium oxide.
5. The method for separating and recovering rare earth and iron from neodymium iron boron waste material according to claim 3, wherein the additive comprises at least one of potassium carbonate, potassium bicarbonate, potassium hydroxide and potassium oxide.
6. The method for separating and recovering rare earth and iron from neodymium iron boron waste according to claim 1, wherein in step S2, the neodymium iron boron calcine is mixed with water according to a mass to volume ratio of 1 (3-8).
7. The method for separating and recycling rare earth and iron from neodymium iron boron wastes according to claim 6, wherein in step S2, the neodymium iron boron calcine is mixed with water, leached for 0.5-4 hours at 60-90 ℃, and filtered, so as to obtain leachate and rare earth oxide.
8. The method for separating and recovering rare earth and iron from neodymium iron boron wastes according to claim 1, wherein in step S3, the leachate is mixed with the oxidant according to the molar ratio of the ferric iron to the oxidant of 1 to (2-6).
9. The method for separating and recycling rare earth and iron from neodymium iron boron wastes according to claim 8, wherein in step S3, the leachate is mixed with the oxidant, and then stirred for 1-4 h at 60-90 ℃ to obtain a sodium ferrate mixed solution.
10. The method for separating and recovering rare earth and iron from neodymium iron boron waste according to claim 1, wherein in step S4, the sodium ferrate mixed solution and the potassium hydroxide solution are mixed according to a volume ratio of the sodium ferrate mixed solution to the potassium hydroxide solution of 1 (1-2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110798810.6A CN113621804A (en) | 2021-07-15 | 2021-07-15 | Method for separating and recycling rare earth and iron from neodymium iron boron waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110798810.6A CN113621804A (en) | 2021-07-15 | 2021-07-15 | Method for separating and recycling rare earth and iron from neodymium iron boron waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113621804A true CN113621804A (en) | 2021-11-09 |
Family
ID=78379909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110798810.6A Pending CN113621804A (en) | 2021-07-15 | 2021-07-15 | Method for separating and recycling rare earth and iron from neodymium iron boron waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113621804A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955230A (en) * | 2010-05-12 | 2011-01-26 | 合肥富通机电自动化有限公司 | Preparation method of potassium ferrate |
| CN103540756A (en) * | 2013-10-29 | 2014-01-29 | 中南大学 | Method for dissolving out rare-earth by treating waste neodymium-iron-boron materials |
| CN109554549A (en) * | 2019-01-24 | 2019-04-02 | 内蒙古科技大学 | The method that high temperature and pressure leaches rare earth in recycling neodymium iron boron waste material |
| CN111020189A (en) * | 2020-01-03 | 2020-04-17 | 连云港高品再生资源有限公司 | Method for extracting ore pulp of neodymium iron boron oxidizing and roasting material |
| US20200140974A1 (en) * | 2018-11-07 | 2020-05-07 | Northeast Normal University | Method of removing iron ions from a solution containing neodymium, praseodymium, dysprosium and iron |
-
2021
- 2021-07-15 CN CN202110798810.6A patent/CN113621804A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955230A (en) * | 2010-05-12 | 2011-01-26 | 合肥富通机电自动化有限公司 | Preparation method of potassium ferrate |
| CN103540756A (en) * | 2013-10-29 | 2014-01-29 | 中南大学 | Method for dissolving out rare-earth by treating waste neodymium-iron-boron materials |
| US20200140974A1 (en) * | 2018-11-07 | 2020-05-07 | Northeast Normal University | Method of removing iron ions from a solution containing neodymium, praseodymium, dysprosium and iron |
| CN109554549A (en) * | 2019-01-24 | 2019-04-02 | 内蒙古科技大学 | The method that high temperature and pressure leaches rare earth in recycling neodymium iron boron waste material |
| CN111020189A (en) * | 2020-01-03 | 2020-04-17 | 连云港高品再生资源有限公司 | Method for extracting ore pulp of neodymium iron boron oxidizing and roasting material |
Non-Patent Citations (1)
| Title |
|---|
| 王亚磊等: ""铁酸钠的制备及应用"", 《轻金属》, no. 5, 21 May 2021 (2021-05-21), pages 11 - 14 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102443701B (en) | Clean metallurgic comprehensive utilization method of iron vitriol slags | |
| CN103540756B (en) | A kind of method processing waste and old neodymium iron boron material dissolution rare earth | |
| CN106129511A (en) | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| CN103374652A (en) | Method for comprehensively recycling rare earth and fluorine in process of treating bastnaesite | |
| CN105603190B (en) | A kind of method that cleaning copper electrolyte reclaims valuable metal | |
| CN105648214B (en) | It is a kind of to control the method that current potential vulcanization separates valuable metal in solution | |
| CN102618719A (en) | Method for directly leaching zinc and recovering gallium, germanium and indium from zinc sulfide concentrate | |
| CN104388711A (en) | Method for recovering rare earth by leaching rare earth oxide molten slag | |
| CN111187927A (en) | Method for selectively sulfating and recovering rare earth in neodymium iron boron waste | |
| CN107299219A (en) | A kind of resource utilization method of electroplating sludge | |
| CN104032131B (en) | Method for processing high-tin anode slurry | |
| CN112458280A (en) | Method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution | |
| Ujaczki et al. | Recovery of rare earth elements from Hungarian red mud with combined acid leaching and liquid-liquid extraction | |
| WO2012171480A1 (en) | Hydrometallurgical method for comprehensive recycling of lateritic nickel ore components as products | |
| Xue et al. | Separation and Recovery of Nickel and Cadmium from Spent Cd—Ni Storage Batteries and Their Process Wastes | |
| JP4215547B2 (en) | Cobalt recovery method | |
| CN113652550A (en) | Method for comprehensively recovering rare earth and iron from neodymium iron boron oil sludge | |
| US20160102383A1 (en) | System and method for the recovery of metal values from slags, drosses, and other metal-bearing materials | |
| CN112981124A (en) | Method for separating and enriching thallium from thallium-containing cobalt oxide waste residue | |
| CN113621804A (en) | Method for separating and recycling rare earth and iron from neodymium iron boron waste | |
| US20230124749A1 (en) | Ammonium complex system-based method for separating and purifying lead, zinc, cadmium, and copper | |
| CN110550664B (en) | Method for preparing iron oxide red by roasting cyanide tailings containing arsenic | |
| CN116377521B (en) | Method for recycling mixed rare earth from NdFeB waste | |
| CN115074530B (en) | Method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under hydrochloric acid system | |
| CN115141942B (en) | Method for recovering rare earth from neodymium iron boron waste and separating main element iron and application of method in preparation of soft magnetic ferrite serving as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211109 |
|
| RJ01 | Rejection of invention patent application after publication |