CN113667823A - Method for comprehensively recovering rare earth and iron from neodymium iron boron waste - Google Patents
Method for comprehensively recovering rare earth and iron from neodymium iron boron waste Download PDFInfo
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- CN113667823A CN113667823A CN202110799769.4A CN202110799769A CN113667823A CN 113667823 A CN113667823 A CN 113667823A CN 202110799769 A CN202110799769 A CN 202110799769A CN 113667823 A CN113667823 A CN 113667823A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 80
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 77
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 75
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 74
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 41
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 17
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 8
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 13
- 239000011734 sodium Substances 0.000 abstract description 13
- 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 abstract description 12
- 229910052708 sodium Inorganic materials 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 11
- 239000002893 slag Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- -1 rare-earth fluoride Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910013868 M2SO4 Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910017557 NdF3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MXCPYJZDGPQDRA-UHFFFAOYSA-N dialuminum;2-acetyloxybenzoic acid;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].CC(=O)OC1=CC=CC=C1C(O)=O MXCPYJZDGPQDRA-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- 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
- C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
-
- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of rare earth and iron recovery, in particular to a method for comprehensively recovering rare earth and iron from neodymium iron boron waste; in the invention, an oxidant is adopted to react with iron in the neodymium iron boron waste material at high temperature to generate sodium ferrate dissolved in water, then water leaching is adopted to dissolve out the sodium ferrate dissolved in water, and oxidized rare earth is not dissolved in water and still remains in slag, thereby realizing the selective separation of rare earth and iron; and then potassium ferrate with high added value is obtained by the reaction of potassium hydroxide solution and leaching solution, thus achieving the purpose of recycling iron; the method has the characteristics of short process flow, good separation effect of the rare earth and the iron and high rare earth recovery rate.
Description
Technical Field
The invention relates to the technical field of rare earth and iron recovery, in particular to a method for comprehensively recovering rare earth and iron from neodymium iron boron waste.
Background
Neodymium iron boron is an excellent rare earth permanent magnet material, and is widely applied in various fields such as computers, communication technologies, aerospace technologies, motor engineering, automobile industry, nuclear magnetic resonance imagers and the like due to the advantages of high remanence, high coercivity, high magnetic energy product and the like.
The manufacturing process of the neodymium iron boron magnet mainly comprises the steps of material preparation, ingot making by smelting/belt throwing, powder making, profiling, sintering tempering, magnetism detection, grinding, cutting, electroplating, finished product production and the like; in the process of neodymium iron boron grinding and cutting, the content of waste materials such as oil sludge, abrasive dust, sawdust and leftover materials generated by cutting and grinding is up to 30%, the content of rare earth elements such as praseodymium, neodymium and dysprosium in the waste materials is up to 20% -30%, the content of iron in the waste materials is up to 60% -70%, and the method has extremely high economic value, so that the method has great strategic significance in deeply separating and recycling rare earth and iron from neodymium iron boron waste materials.
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 comprehensively recovering rare earth and iron from neodymium iron boron waste, which adopts an oxidant to react with iron in the neodymium iron boron waste at a high temperature to generate sodium ferrate dissolved in water, then adopts water to leach out, dissolves out the sodium ferrate dissolved in water, and oxidized rare earth is not dissolved in water and still remains in slag, thereby realizing the selective separation of the rare earth and the iron; and then potassium ferrate with high added value is obtained by the reaction of potassium hydroxide solution and leaching solution, thus achieving the purpose of recycling iron.
The technical scheme for solving the technical problem is as follows:
a method for comprehensively recovering rare earth and iron from neodymium iron boron waste comprises the following steps:
step S1, uniformly mixing the neodymium iron boron waste with an oxidant, and roasting to obtain neodymium iron boron calcine;
step S2, mixing the neodymium iron boron calcine with water, leaching and filtering to obtain leachate and rare earth oxide;
and step S3, mixing the leachate with a potassium hydroxide solution, uniformly stirring, recrystallizing and filtering to obtain the potassium ferrate.
As a modification of the present invention, in step S1, the ratio by mass is 1: (2-6), uniformly mixing the neodymium iron boron waste with the oxidant.
As a further improvement of the invention, in step S1, the neodymium iron boron waste and the oxidant are uniformly mixed and then roasted for 2-6 hours at 200-400 ℃ to obtain the neodymium iron boron calcine.
As a further improvement of the present invention, the oxidizing agent is at least one of sodium peroxide and potassium peroxide.
As a further improvement of the present invention, in step S2, the ratio by mass to volume is 1: (3-8), mixing the neodymium iron boron calcine with water.
As a further improvement of the invention, in step S2, the neodymium iron boron calcine is uniformly 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.
As a further improvement of the present invention, in step S3, the ratio by volume of 1: (1-2), mixing the leachate with the potassium hydroxide solution, and then uniformly stirring.
As a further improvement of the method, the leachate and the potassium hydroxide solution are uniformly mixed, crystallized at the temperature of 0-5 ℃, filtered, and washed for 2-3 times by using the potassium hydroxide solution to obtain the potassium ferrate.
As a further improvement of the invention, the concentration of the potassium hydroxide solution is 40-60 wt%.
As a further improvement of the invention, the potassium hydroxide solution has a concentration of 50% by weight.
In the invention, an oxidant is adopted to react with iron in the neodymium iron boron waste material at high temperature to generate sodium ferrate dissolved in water, then water leaching is adopted to dissolve out the sodium ferrate dissolved in water, and oxidized rare earth is not dissolved in water and still remains in slag, thereby realizing the selective separation of rare earth and iron; and then potassium ferrate with high added value is obtained by the reaction of potassium hydroxide solution and leaching solution, thus achieving the purpose of recycling iron; the method has the characteristics of short process flow, good separation effect of the rare earth and the iron and high rare earth recovery rate.
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 steps 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, domestic, mainly retrieve tombarthite from the neodymium iron boron waste material, nevertheless to occupying the biggest iron resource, do not retrieve, lead to producing a large amount of iron slag or iron-containing waste water, direct stockpiling or discharge not only extravagant iron resource, the polluted environment still has a lot of scholars to carry out the research to the recovery technique of neodymium iron boron waste material at present, as follows:
Lyman（Lyman J. W., Palmer G. R. Recycling of Rare Earths and Iron from NdFeB Magnet Scrap[J]. High Temperature Materials &processes, 1993, 11 (1-4).)2SO4Wherein the pH value is controlled to be about 0.2 to prevent Fe (OH)3After precipitation, NaOH, KOH or NH is added4OH, adjusting the pH value to 1.5-2.0, and filtering to obtain Nd2(SO4)3•M2SO4•6H2O(M＝Na，K，NH4) Dissolving it in HF to obtain rare-earth fluoride NdF3And then rare earth metal can be obtained by a calcium thermal reduction method, although the method better recovers rare earth, the process flow is long, and iron resources in the iron-rich slag are not recovered, so that the comprehensive utilization rate of neodymium iron boron waste resources is low.
Tangjie (Tangjie, Wei Chengfu, Zhao guide, etc. Nd in sintered Nd-Fe-B waste material2O3Recovery of [ J ]]Rare metals and cemented carbides, 2009 (01): 9-11) recovering rare earth from the sintered neodymium iron boron waste by a sulfuric acid double salt method, firstly adding sulfuric acid and sodium sulfate into the neodymium iron boron waste, then converting the rare earth into rare earth sulfuric acid double salt, then precipitating the rare earth by alkali, and firing to obtain high-purity Nd2O3Although the sulfuric acid double salt method can obtain high-purity rare earth oxide, the process flow is long, rare earth oxide can be obtained only by acid leaching, precipitation, calcination and other processes, a large amount of iron-rich slag and iron-containing waste liquid generated in the leaching process are not treated, so that iron resources are wasted, and the comprehensive utilization rate of neodymium iron boron waste resources is low.
The method for selectively leaching the rare earth in the neodymium iron boron oil sludge (CN 108103318A) comprises the steps of firstly burning the neodymium iron boron oil sludge at 700-900 ℃ to remove oil, then adding sulfate in the roasting of the oil-removed neodymium iron boron, roasting at 250-450 ℃ at low temperature, and roasting the roasted product at 550-750 ℃ at medium temperature to decompose ferric sulfate; the roasted product is leached by water to obtain a rare earth sulfate solution and iron red slag, under the optimal condition, the leaching rate of the rare earth reaches over 99 percent, the leaching rate of the iron is lower than 1 percent, and the rare earth in the neodymium iron boron oil sludge is effectively and selectively leached.
In order to solve the above problems, as shown in fig. 1 and 2, the present invention provides a method for comprehensively recovering rare earth and iron from neodymium iron boron waste, comprising the following steps:
step S1, uniformly mixing the neodymium iron boron waste with an oxidant, and roasting to obtain neodymium iron boron calcine;
step S2, mixing the neodymium iron boron calcine with water, leaching and filtering to obtain leachate and rare earth oxide;
and step S3, mixing the leachate with a potassium hydroxide solution, uniformly stirring, recrystallizing and filtering to obtain the potassium ferrate.
In the invention, an oxidant is adopted to react with iron in the neodymium iron boron waste material at high temperature to generate sodium ferrate dissolved in water, then water leaching is adopted to dissolve out the sodium ferrate dissolved in water, and oxidized rare earth is not dissolved in water and still remains in slag, thereby realizing the selective separation of rare earth and iron; and then potassium ferrate with high added value is obtained by the reaction of potassium hydroxide solution and leaching solution, thus achieving the purpose of recycling iron; the method has the characteristics of short process flow, good separation effect of the rare earth and the iron and high rare earth recovery rate.
In step S1, the mass ratio of the components is 1: (2-6), uniformly mixing the neodymium iron boron waste with an oxidant, wherein the oxidant is at least one of sodium peroxide and potassium peroxide, and the mixing ratio is 1: the proportion of (2-6) is not less, the reaction is incomplete when the proportion is less, and the oxidant is wasted when the proportion is more. Uniformly mixing the neodymium iron boron waste with an oxidant, and roasting for 2-6 hours at 200-400 ℃ to obtain neodymium iron boron calcine, wherein the temperature condition needs to be controlled within 200-400 ℃, and the recovery rate of iron can be influenced when the temperature is less than 200 ℃ and more than 400 ℃.
In step S2, the mass to volume ratio is 1: (3-8), mixing the neodymium iron boron calcine with water, wherein the ratio of the neodymium iron boron calcine to the water is 1: (3-8), in order to match with subsequent leaching, uniformly mixing the neodymium iron boron calcine with water, leaching for 0.5-4 h at 60-90 ℃, and filtering to obtain a leaching solution and oxidized rare earth, wherein the temperature condition is required to be within 60-90 ℃, and if the temperature is lower than 60 ℃ and higher than 90 ℃, the recovery of the rare earth and the leaching rate of iron are affected.
In step S3, the volume ratio is 1: (1-2), mixing the leachate with a potassium hydroxide solution, and stirring uniformly, wherein the ratio of the leachate to the potassium hydroxide solution is 1: (1-2), when the ratio is less than or greater than the ratio, the recovery rate of iron is affected; uniformly mixing the leachate with a potassium hydroxide solution, crystallizing at 0-5 ℃, filtering, and washing for 2-3 times by using the potassium hydroxide solution to obtain the potassium ferrate, wherein the concentration of the potassium hydroxide solution is 40-60 wt%, preferably, the concentration of the potassium hydroxide solution is 50 wt%.
Specifically, the method for comprehensively recovering rare earth and iron from neodymium iron boron waste comprises the following steps:
(1) uniformly mixing neodymium iron boron waste with an oxidant according to the mass ratio of 1: 2-6, and roasting at 200-400 ℃ for 2-6 h to obtain neodymium iron boron calcine;
(2) mixing the neodymium iron boron calcine with water according to the mass-volume ratio of 1: 3-8, leaching for 0.5-4 h at the temperature of 60-90 ℃, and filtering to obtain a leaching solution and oxidized rare earth;
(3) mixing the leachate with a potassium hydroxide solution according to the volume ratio of 1: 1-2, uniformly stirring, crystallizing at 0-5 ℃, filtering, and washing for 2-3 times by using the potassium hydroxide solution to obtain potassium ferrate; the concentration of the potassium hydroxide solution is 40-60 wt%;
for a better illustration and explanation of the invention, the following examples are provided:
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.
Example one
(1) Uniformly mixing neodymium iron boron waste with sodium peroxide according to the mass ratio of 1: 2, and roasting for 4 hours at the temperature of 200 ℃ 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, leaching for 3 hours at the temperature of 60 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leachate with a potassium hydroxide solution according to the volume ratio of 1: 1, uniformly stirring, crystallizing at 0 ℃, filtering, and washing for 3 times by using the potassium hydroxide solution to obtain potassium ferrate; wherein the concentration of the potassium hydroxide solution is 40 wt%;
the results obtained in this example one are as follows: the leaching rate of iron is 98.46 percent, and the leaching rate of rare earth is 0.30 percent; the total recovery rate of iron is 96.87 percent, and the total recovery rate of rare earth is 98.78 percent; the purity of the potassium ferrate is 99.15 percent.
Example two
(1) Uniformly mixing neodymium iron boron waste with sodium peroxide according to the mass ratio of 1: 3, and roasting for 5 hours at the temperature of 250 ℃ 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, leaching for 3.5 hours at the temperature of 90 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leachate with a potassium hydroxide solution according to the volume ratio of 1: 1.25, uniformly stirring, crystallizing at 5 ℃, filtering, and washing for 2 times by using the potassium hydroxide solution to obtain potassium ferrate; wherein the concentration of the potassium hydroxide solution is 50 wt%;
the results obtained in example two are as follows: the leaching rate of iron is 99.05 percent, and the leaching rate of rare earth is 0.29 percent; the total recovery rate of iron is 96.88%, and the total recovery rate of rare earth is 98.66%; the purity of the potassium ferrate is 99.23 percent.
EXAMPLE III
(1) Uniformly mixing neodymium iron boron waste with potassium peroxide according to the mass ratio of 1: 6, and roasting for 6 hours at the temperature of 400 ℃ 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, leaching for 4 hours at 90 ℃, and filtering to obtain leachate and rare earth oxide;
(3) mixing the leachate with a potassium hydroxide solution according to the volume ratio of 1: 1.5, uniformly stirring, crystallizing at 0 ℃, filtering, and washing for 3 times by using the potassium hydroxide solution to obtain potassium ferrate; wherein the concentration of the potassium hydroxide solution is 60 wt%;
the results obtained in example three are as follows: the leaching rate of iron is 98.72 percent, and the leaching rate of rare earth is 0.49 percent; the total recovery rate of iron is 96.80 percent, and the total recovery rate of rare earth is 98.45 percent; the purity of the potassium ferrate is 99.16%.
The results of examples one to three are compared as follows:
 |
example one | Example two | EXAMPLE III |
| Iron leaching rate | 98.46% | 99.05% | 98.72% |
| Leaching rate of rare earth | 0.3% | 0.29% | 0.49% |
| Total iron recovery | 96.87% | 96.88% | 96.8% |
| Total recovery rate of rare earth | 98.78% | 98.66% | 98.45% |
| Purity of potassium ferrate | 99.15% | 99.23% | 99.16% |
The invention has the following advantages:
1. the method adopts oxidant to react with ferric oxide at high temperature to generate water-soluble sodium ferrate (or potassium ferrate), then adopts water leaching to dissolve out the water-soluble sodium ferrate (or potassium ferrate), and the rare earth oxide is insoluble in water and still remains in slag, thereby realizing the selective separation of rare earth and iron.
2. The selective separation of the rare earth and the iron in the neodymium iron boron waste is realized by adopting a strong oxidant roasting-water leaching process, sodium salt and potassium salt are added in roasting additives, and the iron is converted into sodium ferrite or potassium ferrite dissolved in acid, or sodium ferrate and potassium ferrate. The rare earth oxide can not react with sodium salt and potassium salt, the leaching rate of iron is more than 98%, the rare earth can not be dissolved out, the leaching rate of the rare earth is lower than 1%, 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; the potassium ferrate product is obtained by the ferrate solution by a replacement-crystallization method, and the purity of the potassium ferrate product is more than 99 percent; the total recovery rate of the rare earth and the iron is more than 96 percent, and the comprehensive utilization rate of resources is high.
Therefore, the method has the characteristics of short process flow, 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 within the scope of the present invention.
Claims (10)
1. A method for comprehensively recovering rare earth and iron from neodymium iron boron waste is characterized by comprising the following steps:
step S1, uniformly mixing the neodymium iron boron waste with an oxidant, and roasting to obtain neodymium iron boron calcine;
step S2, mixing the neodymium iron boron calcine with water, leaching and filtering to obtain leachate and rare earth oxide;
and step S3, mixing the leachate with a potassium hydroxide solution, uniformly stirring, recrystallizing and filtering to obtain the potassium ferrate.
2. The method for comprehensively recycling rare earth and iron from neodymium iron boron wastes according to claim 1, wherein in the step S1, the mass ratio of the rare earth to the iron is 1: (2-6), uniformly mixing the neodymium iron boron waste with the oxidant.
3. The method for comprehensively recycling rare earth and iron from neodymium iron boron wastes according to claim 2, characterized in that in step S1, the neodymium iron boron wastes and the oxidant are uniformly mixed and then roasted for 2h to 6h at 200 ℃ to 400 ℃ to obtain neodymium iron boron calcine.
4. The method for comprehensively recovering rare earth and iron from neodymium iron boron waste according to claim 3, wherein the oxidant is at least one of sodium peroxide and potassium peroxide.
5. The method for comprehensively recycling rare earth and iron from neodymium iron boron wastes according to claim 1, wherein in step S2, the mass to volume ratio of the rare earth to the iron is 1: (3-8), mixing the neodymium iron boron calcine with water.
6. The method for comprehensively recycling rare earth and iron from neodymium iron boron wastes according to claim 5, characterized in that in step S2, the neodymium iron boron calcine is uniformly mixed with water, then leached for 0.5-4 h at 60-90 ℃, and then filtered, so as to obtain leachate and oxidized rare earth.
7. The method for comprehensively recycling rare earth and iron from neodymium iron boron wastes according to claim 1, wherein in step S3, the ratio by volume of the rare earth to the iron is 1: (1-2), mixing the leachate with the potassium hydroxide solution, and then uniformly stirring.
8. The method for comprehensively recycling rare earth and iron from neodymium iron boron wastes according to claim 7, characterized in that the leaching solution is uniformly mixed with the potassium hydroxide solution, crystallized at 0-5 ℃, filtered, and then washed with the potassium hydroxide solution for 2-3 times to obtain potassium ferrate.
9. The method for comprehensively recycling rare earth and iron from neodymium iron boron waste according to claim 8, wherein the concentration of the potassium hydroxide solution is 40-60 wt%.
10. The method for comprehensively recovering rare earth and iron from neodymium iron boron waste according to claim 9, wherein the concentration of the potassium hydroxide solution is 50 wt%.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168926A (en) * | 1996-02-13 | 1997-12-31 | 三德金属工业株式会社 | Method for recovering valuable elements from rare-earth and ferrous alloy |
| US5746994A (en) * | 1996-08-09 | 1998-05-05 | New Mexico State University Technology Transfer Corporation | Method for synthesizing ferrate and ferrate produced thereby |
| CN1559917A (en) * | 2004-02-15 | 2005-01-05 | 云南大学 | Process of synthesizing high titanate and application as dehydrator for algas thereby |
| CN1749166A (en) * | 2005-11-03 | 2006-03-22 | 深圳职业技术学院 | Process for preparing solid potassium ferrate |
| CN1765753A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Potassium ferrate preparation method |
| 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 |
| US20160068929A1 (en) * | 2014-09-08 | 2016-03-10 | Patrick R. Taylor | EXTRACTION OF RARE EARTH METALS FROM NdFeB USING SELECTIVE SULFATION ROASTING |
| CN105568007A (en) * | 2016-01-25 | 2016-05-11 | 江西理工大学 | Method for recovering rare earth from waste rare earth phosphor |
| 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 |
| CN111560520A (en) * | 2020-05-16 | 2020-08-21 | 东华理工大学 | Method for cleanly and efficiently extracting rare earth elements from waste fluorescent powder |
| CN112725622A (en) * | 2020-12-02 | 2021-04-30 | 北京工业大学 | Method for recovering rare earth in waste cerium-based rare earth polishing powder by two-step acid leaching gradient separation |
-
2021
- 2021-07-15 CN CN202110799769.4A patent/CN113667823A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168926A (en) * | 1996-02-13 | 1997-12-31 | 三德金属工业株式会社 | Method for recovering valuable elements from rare-earth and ferrous alloy |
| US5746994A (en) * | 1996-08-09 | 1998-05-05 | New Mexico State University Technology Transfer Corporation | Method for synthesizing ferrate and ferrate produced thereby |
| CN1559917A (en) * | 2004-02-15 | 2005-01-05 | 云南大学 | Process of synthesizing high titanate and application as dehydrator for algas thereby |
| CN1765753A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Potassium ferrate preparation method |
| CN1749166A (en) * | 2005-11-03 | 2006-03-22 | 深圳职业技术学院 | Process for preparing solid potassium ferrate |
| 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 |
| US20160068929A1 (en) * | 2014-09-08 | 2016-03-10 | Patrick R. Taylor | EXTRACTION OF RARE EARTH METALS FROM NdFeB USING SELECTIVE SULFATION ROASTING |
| CN105568007A (en) * | 2016-01-25 | 2016-05-11 | 江西理工大学 | Method for recovering rare earth from waste rare earth phosphor |
| 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 |
| CN111560520A (en) * | 2020-05-16 | 2020-08-21 | 东华理工大学 | Method for cleanly and efficiently extracting rare earth elements from waste fluorescent powder |
| CN112725622A (en) * | 2020-12-02 | 2021-04-30 | 北京工业大学 | Method for recovering rare earth in waste cerium-based rare earth polishing powder by two-step acid leaching gradient separation |
Non-Patent Citations (1)
| Title |
|---|
| 林河成: ""从钕铁硼磁体废料制取氧化钕的研究"", 《矿冶》, vol. 6, no. 1, 31 March 1997 (1997-03-31), pages 63 - 66 * |
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